At Heathrow the post office is located in terminal 3
http://www.heathrowairport.com/heathrow-airport-guide/services-and-facilities/postal-services
There are post boxes located in all terminals both before and after security. Anything posted can be inspected by HMRC.
Also the postboxes at Heathrow are size limited so only letters can be posted.
Below is a screen grab from the post office website. It details the opening times. Current as of 24/May/2015
Also you can purchace books of postage stamps at branches of WHSmith located in all terminals
There is a Post Office branch in Heathrow Terminal 3.
Photo at https://flic.kr/p/iZidNM
It is open every day but only 5 hours on Sundays, from 9 AM to 1 PM. Walking directions are here
Credit:stackoverflow.com‘
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