Hey James,
Might be possible, although if it is, the roads in eastern Angola would be rough going to say the least. Probably good adventure though.
Having said that, even if it is doable logistically, not sure I'd recommend missing Botswana and Namibia and South Africa for what a person would gain by cutting across and heading up the west coast. Those are pretty spectacular places and a destination in their own right.
There is a ton of stuff to see down south and many route options. For example, you can also consider heading down into Malawi and then cutting across Zimbabwe instead of crossing Zambia.
The attraction of riding back home is certainly understandable. However due to a lot of reasons including how good the riding in South Africa is, the vast majority get to Cape Town, see how the desire levels are and funds are holding out and then decide from there to ship back, turn north and keep riding or some take a third option which is to leave the bike and fly home, save more money and then return for another trip back
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