Mthembu completed the ultra-distance race in 6:24:05* to secure the silver medal, clocking a new national record by bettering the previous SA mark of 6:25:07 set by Bruce Fordyce in Stellenbosch in 1999.
He also became the first SA man to step on the podium at the annual event since Cornet Mathomane grabbed bronze in Torhout 1993. Mthembu, who took the lead in the latter stages of the race, was overtaken by Hideaki Yamauchi with less than 10km remaining, and the Japanese athlete took the win in 6:18:22.
Gift Kelehe finished ninth in 6:43:00 and Comrades Marathon 'down' run record holder David Gatebe was 12th in 6:44:34, with the SA squad taking gold in the team category (top three athletes to count) ahead of Japan and the United States, who ended second and third respectively.
Rufus Photo ended 19th in 6:52:43, and fellow early leader Ludwick Mamabolo was unable to finish the race.
"Congratulations to Bongumusa Mthembu on his fine performance, and to the whole team for a superb all-round effort," said Athletics SA president Aleck Skhosana.
"South Africa has a rich history in ultra-distance running, and hosts some of the most popular and prestigious races in the world, so it is fitting to have our athletes competing at the highest level and carrying the national flag with pride by achieving their goals.