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1.
Time for Pimm's (posh cocktail made with pimm's, lemonade, and fruit).

Implies lazy, happy days sitting in the sun with nothing to do and no need to worry about time.
Is it pimms o' clock yet?
by the pimm's monster May 09, 2008
 
2.
An exclamation of when something is excellent or very good. Originating from the advert of Pimms (British Drink, traditionally associated with tennis and the posh).
A day off from work? To go skydiving? On a Friday? Pimms o' clock alright.
by Kent, England June 06, 2005
 
3.
When a typically English situation calls for the pleasant taste of Pimms.
"Picnic blankets? Mums and dads? It's Pimms O' Clock!"

"Wedding party? Embarrassing dancing? It must be Pimms O' Clock!"
by FineAndDandy May 02, 2010
 
4.
Used when about to shoot at goal in a British football match, to both alert team-mates and scare opposition.
Also used as a exclamation when celebrating a goal.
James: Pimms O' Clock! (fires a soaring shot over the bar)
Dan: Maybe not quite yet then.
by Jimbozi July 14, 2008