The current version of PL/Python functions as a trusted language only; access to the file system and other local resources is disabled. Specifically, PL/Python uses the Python restricted execution environment, further restricts it to prevent the use of the file open call, and allows only modules from a specific list to be imported. Presently, that list includes: array, bisect, binascii, calendar, cmath, codecs, errno, marshal, math, md5, mpz, operator, pcre, pickle, random, re, regex, sre, sha, string, StringIO, struct, time, whrandom, and zlib.
Read the upstream documentation. For corrections, first check the current manual.