Kapoor joined various dignitaries at the opening of the South African parliament here Friday.
"On behalf of our government and all our people, I extend our heartfelt welcome to all these distinguished guests and thank them for honouring our nation today by their presence on this important national occasion," Mbeki said in his opening address of the joint sitting of parliament.
"I am honoured to acknowledge the presence in the gallery of an outstanding human being and friend of our country and people, the leading Indian Bollywood actor, Anil Kapoor.
"All of us are deeply moved that Anil Kapoor, a citizen of the beloved land of Mahatma Gandhi, has agreed to serve as one of South Africa's global brand ambassadors, committed to mobilise the peoples of the world to support our efforts to make a success of our liberation."
Kapoor has earlier admitted to having a soft spot for South Africa after first coming here about 15 years ago to shoot for a film. Since then, he has been a frequent visitor to South Africa for business and private reasons.
Last year, Kapoor told the emotions he experienced during his first meeting with world icon Nelson Mandela could only be compared with the birth of his first child.
The actor could not be reached for comment as he was in transit, returning home after spending almost a fortnight here. Last week, he was supporting the Indian team at the inaugural A1 Grand Prix of Nations in Durban. Kapoor is one of the founders and the president of A1 Team India.
As private organisations and the government here prepare for celebrating the centenary of the birth of Mahatma Gandhi's Satyagraha initiatives later this year, the Indian leader also came under the spotlight in Mbeki's address.
"(Also present here is) Ella Gandhi, (the South African) granddaughter of the irreplaceable Mahatma Gandhi, who 100 years ago here in South Africa, launched Satyagraha, the unique non-violent struggle that liberated India and inspired millions of freedom fighters everywhere else in the world," Mbeki said.