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Looking through the bios of associates on a couple of firms' sites I noticed that many of them did not begin work at the firm straight out of law school. How does one typically obtain employment at a big firm after a couple years of experience elsewhere?

They probably clerked or worked at another biglaw firm and lateraled over. It's my impression that it's hard to go from a small/mid-sized firm/government (except DOJ honors maybe) to a big firm.

...But you should ask them! Email them (especially if you share an alma mater or something) and say you'd like to get coffee and talk about their career path. If you're trying to gather info in advance of OCI, maybe set up a phone call since those are probably easier to schedule than an in-person meeting.

stalk them on Linkedin via Google is probably the easiest.