Sample database for PostgreSQL
I just published a PostgreSQL port of the Open Source Shakespeare database: https://github.com/catherinedevlin/opensourceshakespeare. It's much more fun than all those other sample databases.
There's a PgFoundry project that contains several example PostgreSQL databases. Most of these haven't been updated for a while, but will still work with recent PostgreSQL versions.
If you need a bigger database, the MusicBrainz music metadata database has full database dumps available for download.