Record-breaking distance runner Haile Gebrselassie competed for the first time and went on to take the men's title.
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.
The current mark of two hours three minutes 59 seconds was set by Ethiopian Haile Gebrselassie in Berlin in September 2008.
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.
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.
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.
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.
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.
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