Apart from select statements you can use the following commands on psql prompt -
\d [NAME] describe table, index, sequence, or view
\d{t|i|s|v|S} [PATTERN] (add "+" for more detail) list tables/indexes/sequences/views/system tables
\da [PATTERN] list aggregate functions
\db [PATTERN] list tablespaces (add "+" for more detail)
\dc [PATTERN] list conversions
\dC list casts
\dd [PATTERN] show comment for object
\dD [PATTERN] list domains
\df [PATTERN] list functions (add "+" for more detail)
\dg [PATTERN] list groups
\dn [PATTERN] list schemas (add "+" for more detail)
\do [NAME] list operators
\dl list large objects, same as \lo_list
\dp [PATTERN] list table, view, and sequence access privileges
\dT [PATTERN] list data types (add "+" for more detail)
\du [PATTERN] list users
\l list all databases (add "+" for more detail)
\z [PATTERN] list table, view, and sequence access privileges (same as \dp)