POSIX 1003.1-2008 is now available on the web (all 3872 pages of it, in PDF and HTML). You have to register (free). I got to it from the Open Group Bookstore.
See How to Portably scanf into a pid_t in C for my original answer that included this information.
Strictly speaking, the definitive list of the POSIX functions is the POSIX standards documents themselves.
There's a pretty good introduction to what POSIX is all about, with links to plenty of reference material on Wikipedia.
zipped versions of the HTML for grepping
Those are useful when you start wanting to grep for things, without paying for the PDF.
Mentioned by Jonathan.
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