Yes, but the buyer can only request a cancellation.   You still have to issue one.   You can do that on your orders page - click on the dropdown menu arrow alongside the item and select Cancel order > Buyer asked to cancel.   If they've paid a refund will be issued in the process.    Then relist for them to buy again.  

Also see "Proof of collection" on here:
https://www.ebay.co.uk/help/selling/posting-items/setting-postage-options/local-collection?id=4181