All the core, base, alternate, and prestige classes from the SRD will be allowed, see http://www.d20pfsrd.com/classes. If you want to take levels in a class from a third-party product or a 3.5 edition source, let's sit down and look it over to make sure it's not over or under powered, or a game breaker. I will permit most most options, but reserve the right to do some tweaking if there are issues.
As stated on the Races page, I will be revamping Race levels, Monster levels, Template levels, and Undead levels for PC use. If you have something you are considering, let me know so I can get that ready and discuss it with you.
I have the playtest copy of the Advanced Class guide, but haven't read it yet. If you are excited about options from there please let me know so I can get familiar with the new rules.
Base Classes
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Alchemist
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Cavalier
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Gunslinger
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Inquisitor
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Magus
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Oracle
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Summoner
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Witch
Core Prestige Classes
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Arcane Archer
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Arcane Trickster
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Assassin
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Dragon Disciple
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Duelist
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Eldritch Knight
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Loremaster
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Mystic Theurge
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Pathfinder Chronicler
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Shadowdancer
Many others available from Paizo, see the SRD
The Classes page is not final just yet.
NPC Classes
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Adept
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Aristocrat
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Commoner
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Expert
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Warrior
NPC+ Classes (Details coming soon)
Closer to the PC classes, but not quite as powerful - still, may be worth considering a level or two for multiclassing
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Noble
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Spellcrux
Alternate Classes
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Antipaladin
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Ninja
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Samurai