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Evans and George won the 83km sixth stage in three hours, 38 minutes, five seconds (3:38.05), finishing nearly seven minutes ahead of fellow South African Burry Stander and his Swiss partner, Christoph Sauser.
Stander and Sauser, however, retained their overall lead, more than 25 minutes ahead of Evans and George who moved up to second place.
Evans admitted they did not expect to catch the defending champions in Sunday's final stage, a 64km leg to Lourensford wine estate.
"It's really good to get a win but even better to be on the overall podium," Evans said.
"This year was such a rollercoaster ride for us.
"We'll be happy with finishing in second place and will work with that.
"The cheering and support are amazing. Today was very tough and hard, but we're feeling positive and will definitely have enough in the tank to get to Lourensford."
George said they hoped to stay on the podium, but it was more important to ensure they got through the final stage.
"We're ecstatic with the victory. It was so emotional, and winning the stage meant so much," George said.
"We came out fighting for the win. It was our intention to win this stage.
"There is still one stage to go and it'll be important to race, but at the same time ride within ourselves."
Stander said he and Sauser had let the South African duo go when they realised they meant business, but he hoped he and Sauser would pick up another win in the final leg.
"We didn't set the pace today and just followed," Stander said.
"They wanted to prove something and it's always hard to beat a team with a mindset like that. We just kept our own pace.
"We're still feeling strong and look forward to a cracker of a last day to Lourensford.
"We don't know if we'll win the stage, but we'll definitely try."
Meanwhile, Sally Bigham and Esthüer Süss extended their overall lead in the women's race.
Bigham and Süss stretched the gap to a little more than 47 minutes over second-placed Theresa Ralph and Nina Gässler.