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1st look into shapeshifting
http://www.youtube.com/watch?v=ulFPTSOXun0 on that video as you can see the skill allow you to transform on enemies it looks like theres not a timer and the new journal will record what you hunt and can transform into at the min 2:39 the end of the list has npc selections where its shown Eirawen scathatch, the puppet npc seller or crafter, Portia and for some reason Failgus. You can transform into them? O.O not sure but that would be fun. ill certainly head to rank this skill instead of puppetry cuz str and dex are the lower stats i have :p.
Yes, there are some NPCs that can be transformed into. Also, I believe you have to kill a monster X number of times (the journal will tell you) before it is registered and you can transform into it (but there's only a chance that it will count?). There's limited skills available when transformed, but I think you also get stat boosts from each monster that you have collected (however, they are only available when transformed). Some of the boosts are specific to its respective transformation, while some are applied no matter what monster you've changed into.
This is just what I've read about it when it was in the Korean test server, though.