psql (9.1.4)
Type "help" for help.
richardh=> show timezone;
TimeZone
----------
GB
(1 row)
richardh=> set timezone='UTC';
SET
richardh=> show timezone;
TimeZone
----------
UTC
(1 row)
richardh=> set timezone='US/Eastern';
SET
richardh=> show timezone;
TimeZone
------------
US/Eastern
(1 row)
richardh=> set timezone='blah';
ERROR: invalid value for parameter "TimeZone": "blah"