By default MS Office 2010 installs the 32-bit version of itself, so the 32-bit ODBC driver must be used.
- Install the latest PostgreSQL ODBC driver (psqlODBC) from http://adf.ly/1FWF3u
- Run the 32-bit ODBC Data Source Administrator Control Panel (C:\Windows\SysWOW64\odbcad32.exe)
- Add a new "User DSN" as type PostgreSQL Unicode
- Run MS Access and select the DSN from inside "EXTERNAL DATA" tab => ODBC Database.