Scores of foreign dignitaries have already arrived in the country for the memorial service at the 95,000-seat FNB Stadium, where Mandela made his last major public appearance during the 2010 football World Cup.
President Mukherjee will lead a high-level delegation to the memorial service of the former South African President, who died at the age of 95 on December 5.
The delegation will comprise UPA Chairperson Sonia Gandhi, Leader of Opposition Sushma Swaraj, Union Commerce Minister Anand Sharma, CPI-M leader Sitaram Yechury and BSP leader Satish Mishta, a Rashtrapati Bhavan spokesman said in New Delhi.
There has been an "unprecedented interest" to attend the revered statesman's funeral, South African Foreign Minister Maite Nkoana-Mashabane told a news conference here.
The other dignitaries who have confirmed their attendance include French President Francois Hollande and British Prime Minister David Cameron.
Obama today left for South Africa with his wife, Michelle, on board Air Force. Former President George W Bush was also on the plane, along with former first ladies Laura Bush and Hillary Clinton.
Former President Bill Clinton will be reaching South Africa from Rio de Janeiro and former President Jimmy Carter also planned to join the group here.
Palestinian leader Mahmud Abbas, Sri Lanka President Mahinda Rajapaksa, Bangladesh President Abdul Hamid and UN Secretary General Ban Ki-moon will also attend the event. Britain's Prince Charles will represent Queen Elizabeth II at the memorial service.
At least 91 heads of state have already confirmed their attendance and more were believed to be coming, officials said.