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To join the Thieves Underground, you'll first have to learn of its existence. You can do that by talking to Lukan the Witless in Shrouded Hills, or by completing the Pettibone quest in Tarant. Either way, you'll have to talk to the thief beside the Pettibone residence (#1). He'll tell you to speak with Thaddeus Mynor (#2), and once you do that and complete his quest to steal a map of the sewers from the Department of Water (#3), you'll become a member of the Underground. Then you'll get a series of quest to steal objects around the city.
You can have up to four quests open at any one time, and you can get quests from any thief in the city. However, the thief circling the block where Mynor's residence is located is the easiest one to use since he's so close to the fence (#4). Another easy thief to find is the halfling woman in Vermillion Station (#5). To complete quests after stealing the required objects, just hand them over to the fence.
Here are the objects to steal:
a) Cassie's Jewelry (Madam Lil's). The jewelry is in a chest in a back room. You'll have to sneak around or kill Winno Whitewash to open the chest. When you turn in the jewelry you'll receive 1500 experience and 400 gold.
b) Dwarven Rubies (Dock). The rubies are in a locked barrel at the end of the dock, next to the easternmost of the two ships. Just wait for the patrolling dockhand to move away and then pick open the chest. You'll receive 1200 experience and 500 gold.
c) Enchanted Looking Glass (Pettibone Residence). The looking glass is locked in a chest. The easiest way to get it is to enter the residence before talking to Cassandra Pettibone about the elven funerary stone. Then no one will be home. Otherwise you'll have to prowl around to avoid detection, or kill Cassandra and the guards she calls. You'll receive 1000 experience and 100 gold.
d) Essence of Will-o-the-Wisp (H.T. Parnell's). The essence is locked in a chest in Parnell's bedroom. Parnell is involved in a few quests, so you should avoid killing him if possible. When you fence the essence, you'll receive 1000 experience and 200 gold.
e) The Heron Device (Bates Warehouse). The guard out front has the key to the warehouse. So either steal the key from him, or else move as far away from the front door as possible, and then cast the unlocking cantrip on it. Or wait until night when the guard leaves and then pick open the door. Once inside, you'll find the heron device in the back room. When you deliver it to the Underground, you'll receive 1700 experience and 500 gold.
f) Jewel of Hebe (Panarii Temple). It's in the locked chest next to the priest. If you have the unlocking cantrip, then you can stand at the far end of the room and cast the spell on the chest, and the priest won't notice. When you turn in the jewel, you'll receive 1600 experience and 500 gold, but realize that the jewel is a pretty good necklace (+2 beauty, +1 charisma), and so you might want to keep it for yourself.
g) Lethe Wyvern Venom (Zoological Society). It's in a chest in Tristan Fenwick's office. Sneak around or kill Fenwick to open the chest. The venom is worth 1000 experience and 200 gold.
h) Lucky Medallion (Poone's Flophouse). The medallion is being carried by a man in a pink suit. He circles the block where Poone's Flophouse is. Once you rob him or kill him to get the medallion (which gives +2 to your gambling skill), you'll receive 1000 experience and 150 gold.
i) Music Box (Madam Lil's). Madam Lil is carrying the music box. When you steal it from her and turn it in, you'll receive 1700 experience and 150 gold. Madam Lil gives some quests, so if you're going to kill her to get the music box, complete her quests first.
j) Napha Water (Halster Residence). The water is locked in a nightstand next to the bed. If you decide to kill Mrs. Halster to get to the water, make sure you've completed Madame Lil's quests first. When you turn in the napha water, you'll receive 1000 experience and 150 gold.
k) Plans for Schreck's Multi-Barreled Pistol (Bates Engine Factory). The plans are in a locked cabinet on the eastern side of the factory. The easiest way to get the plans is to go into the factory when you get the quest to protect Bates' steam engine prototype, and then steal the plans while you're there. Otherwise, you'll need to open the door at the back of the factory, and then sneak inside and steal the plans when none of the guards is looking. The plans aren't real schematics (you can't use them), so there isn't any reason not to turn them in. When you do turn them in, you'll receive 1500 experience and 400 gold.
l) Potion of Darkest Power (Fitzgerald residence). The potion is in the chest next to the bed. But realize Fitzgerald is the Spot Traps Master, so don't kill him to get the potion if you plan to pursue that skill. The potion is worth 1700 experience and 500 gold.
m) Ring of Virility (Franklin residence). Franklin is wearing the ring, which gives a bonus of +2 CN. If you decide to turn in the ring rather than keep it for yourself, you'll earn 1700 experience and 200 gold.
n) Sword of the Derian Ka (Appleby residence). It's in a safe in the back room, but you can make as much noise as you want opening the safe and Appleby won't mind. The sword is simply a faster version of a regular sword, so it's not very valuable. When you turn it in you'll receive 1500 experience and 500 gold.