Dark Souls might not seem like the type of game to do NPC quests, however you'll often encounter characters in different locations who have various threads you can follow.
An exhaustive list is difficult - there are many variables, and it entirely depends on how you play the game - so we're going to concentrate on four key quests worth investigating - Solaire of Astora, Siegmeyer of Catarina, Lautrec of Carim and Rhea of Thorolund.
Meanwhile, we have explainers on how to access DLC Artorias of the Abyss, the best gift and best class in Dark Souls, Dark Souls' best weapons, Dark Souls Covenants, Dark Souls Estus Flasks locations, Dark Souls Titanite Slab locations and NPC quests including Lautrec of Carim.
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Solaire of Astora quest
Solaire of Astora is likely to be one of the first NPCs you encounter in Dark Souls, you will first find him after defeating Taurus Demon in the Undead Burg. Speak to him enough and agree to his question and he will give you a White Sign Soapstone. This is the last time you really need to bother finding Solaire for a while, although you can also find him at the Sunlight Altar in the Undead Parish, where you can also join the Warriors of Sunlight.
Next, you will want to speak to him at the second Anor Londo bonfire, we recommend that you talk to him here, in order to advance to the next stage of his questline, you will also be able to summon him to fight Ornstein and Smough.
Here is where it gets a little bit complicated. After defeating the Centipede Demon in Demon Ruins, you will find a bonfire with him sitting next to it. However, do not advance into Lost Izalith.
Instead, join the Chaos Servant Covenant, level it up to +2 and head back to where the boss fog door was for the Demon Firesage, to the right are branches that lead to a shortcut to Lost Izalith. Here, there are bugs that you will find, but we're going to be after one with red eyes that will drop a Sunlight Maggot. Once you have done this, you have saved Solaire from going hollow.
If you do not do this, when you open the shortcut you will be greeted by Solaire, having gone hollow in Lost Izalith and have to kill him. If you are successful, you will be able to find Solaire's Summon Sign in the Kiln of the First Flame and he will help you to defeat Gwyn.
Siegmeyer of Catarina quest
You will first encounter Siegmeyer of Catarina outside of Sen's Fortress before you have rung both bells. Talk to him and exhaust all of his dialogue here. Then, once you have run both bells and have headed to Sen's Fortress, you will want to head to where you will first encounter an outdoor area with a rolling boulder, there will be a ledge you can drop down onto. Speak to Siegmeyer here and clear Sen's Fortress. This is a mandatory step, or else you might miss him.
After getting to Anor Londo, you will need to find the outdoor platform with a few silver knights, to the left will be a walkway headed down, here you will find Siegmeyer pinned down by knights in the room ahead. Kill these knights and talk to him, and you will get a Tiny Being's Ring.
From here, if you warp back to Firelink, you will find him, speak to him here and tell him that you opened the gate to Sen's Fortress. Then, he will give you a Miracle. From here, he will head to Blighttown. Before anything else, you will need to free his daughter Sieglinde from a Golden Crystal Golem at the entrance to the Crystal Caves.
Then, Sieglinde will move to Firelink Shrine, where you will be able to speak to her. Reply 'Yes' to her and continue. Then, ensure you have 3 Purple moss clumps and head to Blighttown to the second bonfire. To the left near the Giant Leeches, you'll find Siegmeyer asleep. Respond yes to him and you will give him some moss and he will give you his Shield. Then, head to Lost Izalith
In Lost Izalith, you will encounter a room with a collapsing floor, walk around the back and you will see Siegmeyer overlooking a large hole. You will need to speak to Siegmeyer and let him jump down into the hole with the Toxic Monsters. Here, you will have to follow him and jump down to save him. Ensure he finishes the fight with more than 50% Health or else the story will not continue.
From here, you will need to head back to Firelink Shrine, where you will once again encounter Sieglinde. After speaking with her here, head to Ash Lake. At the first bonfire, speak to her again and she will give you a Titanite Slab.
Lautrec of Carim quest
In the Undead Parish, you will encounter Knight Lautrec of Carim in the upper floor of a Church, which you will be able to unlock him from with a key on the same floor. If you set him free and let him live, you will continue his story and he will return to Firelink Shrine sitting opposite the Firekeeper. He can also offer you tips on where to find some other characters.
However, we highly recommend you kill him instead. Free him from his cell, and get scrapping. He can parry and get around shields, so this will be a tough fight. Lure him all the way back to the courtyard and to the wooden bridge.
Here, you're going to try to kick him off the edge. Do this, quit out of the game and reload to get your spoils: The Ring of Favour and Protection and 5 Humanity, these will be in his cell. If you leave him to live, you can kill him at Firelink - but under no circumstances let this guy live.
If you decide otherwise, after you ring both Bells of Awakening or pick up two Fire Keeper Souls from the Undead Parish and Blighttown, he will kill Anastacia the Firekeeper in Firelink Shrine. This is less than ideal and a very arduous storyline to follow with very little payoff.
If he has killed the Firekeeper, you will find a Black Eye Orb where she was. Now, you will need to get to the boss of Anor Londo, where the Orb will quiver. Use it, and you will invade his world, where he will also have two guards. This is a difficult fight as Lautrec can attack through shields. Kill him, and you will be able to get a Fire Keeper Soul to restore Anastacia and gain access to the Firelink Bonfire once again. Phew!
Rhea of Thorolund quest
After killing Capra Demon, you will find Rhea of Thorolund, talk to her and then she and her team will proceed to the Tomb of the Giants. In there, head just past the first bonfire towards Patches and head into where he kicks you down, kill her hollowed guards and she will give you a replenishment Miracle.
Then, if you want to save her- kill Petrus of Thorolund. If not- after killing any boss after the second bell she will die in the Undead Parish. From here, you can get her Ivory Talisman from Petrus of Thorolund by confronting and killing him.