The victory kept South Africa's hopes of a Grand Slam alive after they brushed aside Ireland last weekend.
South Africa were 17-9 behind at the break but scored 17 unanswered points in the space of seven minutes to grab the initiative from Wales.
Wales refused to cave in and mounted a fierce late rally but couldn't breach the green wall.
"I'm very proud of the boys, they showed great character," said Matfield. "Wales put us under pressure and it was a great game for the spectators to watch.
"Well done to Wales, they really came out and played well. "(Defending) is something we really worked hard on (in training) and it came through and we were happy with that," he added.
Referring to a possible Grand Slam, Matfield said: "I don't know. There's still a fair way to go. We're focusing on Scotland and that's going to be another huge game. We will enjoy tonight and then start fresh from zero on Monday again."