Zimbabwe prime minister Morgan Tsvangirai said in a statement he was "deeply saddened at the death of a footballing legend, Adam Ndlovu" in what he called a "horror crash".
He said: "My prayers are with the Ndlovu family, the football fraternity and the nation at this sad loss."
The brothers were travelling to Victoria Falls to take part in a charity match and were in Peter Ndlovu's SUV when it veered off the road around 12 miles from the famous waterfall.
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The pair, including a man in his 50s, were struck around midday on the Pen y Fan mountain range in Powys, mid-Wales.
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