Record-breaking distance runner Haile Gebrselassie competed for the first time and went on to take the men's title.
Gebrselassie was fulfilling a long-time promise made to race chairman Brendan Foster by taking part in the race.
Theron will be joined in Cape Town by England football star David Beckham and Ethiopian athletics legend Haile Gebrselassie.
Double Olympic champion Haile Gebrselassie failed to finish after suffering an asthma attack.
Gebrselassie has broken 27 world records during an illustrious career, and collected two Olympic gold medals and four world titles.
The current mark of two hours three minutes 59 seconds was set by Ethiopian Haile Gebrselassie in Berlin in September 2008.
"At around the halfway point I felt I could get the record - I felt comfortable the whole way, " said Gebrselassie.
Kenya's Martin Lel won the men's race in an upset for favourites Haile Gebrselassie and reigning world marathon record holder Paul Tergat.
Haile Gebrselassie will show up for a shorter race, but as an asthmatic, he says he will not risk running the marathon.
Meanwhile, two-time Olympic champion Haile Gebrselassie broke the seldom-attempted one-hour world record.
Gebrselassie is, by common consent, the finest distance runner of all time.
Last year, Ethiopian athlete Haile Gebrselassie won the men's race for a fifth time, while the women's race was won by Kenyan Linet Masai.
Marathon world record holder Haile Gebrselassie can run a mile in an astonishing four minutes, 45 seconds, and repeat the performance 26 times in a row.
Haile Gebrselassie poses for photographs afterwards with the media, who have abandoned their usual cynicism in favour of unadulterated fawning in front of the greatest distance runner of all time.
Also on stage will be Beckham, who has scored in three consecutive World Cups, multiple world champion Gebrselassie and Makhaya Ntini, the first black cricketer to play for South Africa.
Co-produced by Terrence Malick and directed by the British documentarian Leslie Woodhead, this is a serious and surging account of the life and times of the Ethiopian track star Haile Gebrselassie.
The issue with Gebrselassie, I think, it's doubtful the floodgates will open with other athletes bailing out of the Olympics, Steve, just because the Olympics are so important to these athletes.
South Africa's Oscar-winning actress Charlize Theron brought a touch of Hollywood glamour to proceedings, alongside England midfielder David Beckham, Ethiopian athletics legend Haile Gebrselassie and Springboks rugby union captain John Smit.
Gebrselassie covered 21.285km to beat Arturo Barrios' long-standing mark.
Earlier in the day, marathon world record-holder Haile Gebrselassie, 35, will hope to triumph in the Great Manchester Run, an event which he won in 2005 in a then-record time of 27 minutes 25 seconds.
"This is a race I have always wanted to compete in and I'm really looking forward to running as it has a worldwide reputation for not only the quality but also the fantastic size of the field, " added Gebrselassie.
There are moments here that are perhaps too ravishing for their own good the beauty of the domestic scenes inside the family hut is like an antidote to the brute facts of poverty and yet, finally, it is impossible not to be stirred by the fluid, frictionless travelling shots of Gebrselassie in motion.
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