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Sometimes, if the depot has a backlog they will deliver for no extra charge on a Saturday, but it is unusual as they don't want people to get to expect it as the norm.
What a lot of people don't know if if you use the Post Office Special Delivery services on a Friday, the mail will not be dleivered until Monday - the next business day so sometimes, if posting on a Friday, it is better to just use first class and hope for the best if you really want it on the Saturday!