I have found Apples to Apples (fsync off in PgSQL) and doing key/value store in PgSQL, PgSQL performed on par with, or slightly faster than MongoDB, using my admittedly not fully baked KVPBench app - http://github.com/gmr/kvpbench.
Setting "synchronous_commit = off" nets you 99.9% of the performance improvement without the possibility of corrupting your entire database.
http://www.flickr.com/photos/gavinmroy/4638958958/
And the presentation it came from: