The figure is a 26% increase on the previous record on 4.17 million hl achieved in 2012, with shipments to the UK driving the growth.
It is the largest market for South African export, accounting for more than a fifth of total volumes in 2013.
Exports to the UK rose 21% to 1.11 million hl.
Wines of South Africa’s chief executive Siobhan Thompson said: “It is encouraging that strong gains were achieved in the UK and Germany, our two biggest markets, where packaged wines in particular showed very healthy growth. Packaged wines to the UK were up 31 per cent and Germany saw an increase of 17 per cent. At the same time, exports also grew across an increasingly broad range of other markets.”
Thompson attributed the growth to a bountiful harvest in 2013, which saw South Africa plug gaps left by poor harvests across Europe.
White wine exports rose by almost 18% and reds were up 22%. Sauvignon Blanc, Cabernet Sauvignon, Shiraz, Pinotage and Merlot saw the largest increases in volume exported.