Your selection of bikes for rent (or purchase) should be far better in South Africa, or possibly you could find something in Namibia as well.
Crossing borders on a bike rented fro Johannesburg worked for me (with an authorisation letter), but this was in 2002, I dont know if it still would. But I did all countries south side of Angola,DRC,Tanzania... Fabulous rides. Main roads should be ok, though maybe not in Angola or northern Mozambique.
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