Sorry I can't remember which forum post had this query in.
send.royalmail.com/ allows you to buy postage from your home by card or Paypal and print the label at home, assuming of course you have a printer. For tracked services someone will have to take it to a post office though. If you can risk sending not tracked eg have plenty of time to send, check arrival by phone and resend if necessary, you can post in a postbox.
I discovered this when looking anxiously for the arrival of my letter posted tracked Thurs teatime, which should have arrived today latest but still hasn't, sigh.. maybe a warning to all not to rely on First Class tracked now to be as fast as it used to be if you are tight on a form return deadline.
Hope this helps,
Denby