The 62-year-old South African was the last of five candidates to address the 207 voting members.
His charisma was on full show in the 15-minute speech, which he ended by announcing he would not take part in the ballot.
Sexwale said: "My campaign ends today and I suspend my participation. I leave only four people."
Blatter was voted in on five occasions, including last May. But he stepped aside days later amid allegations which led to a six-year ban from football-related activity, which he is contesting.
His resignation prompted the world governing body’s extraordinary congress in the most pivotal period of FIFA’s 112-year history.
The successful candidate will serve the remaining term of office for which Blatter was elected last May, meaning there will be a further election in 2019.
Jordan’s Prince Ali bin al Hussein, Sheikh Salman bin Ibrahim al Khalifa of Bahrain, UEFA general secretary Gianni Infantino, and Jerome Champagne, a former FIFA deputy secretary general from France, were the remaining candidates as the first round of voting, estimated to take one hour, 40 minutes began.
The quartet were vying for 207 votes from FIFA’s member associations (Kuwait and Indonesia are suspended).
A two-thirds majority (138 votes) was required for a result in the first round, with a simple majority (more than 50 per cent) needed in subsequent rounds.
Sexwale’s chances of success were slim, ever since his home confederation, the Confederation of African Football, announced its intention to back Sheikh Salman. Infantino and Prince Ali also expect to have support from the region.
His was a low-profile campaign, in contrast to some of his rivals, although he took Infantino to Robben Island earlier this week, sparking suggestions of an alliance.
Sexwale is a former anti-apartheid activist who was imprisoned on Robben Island with Nelson Mandela.
The mining magnate was part of the organising committee for the 2010 World Cup in South Africa.
He said there would be a "party" if any of his four rivals was elected and "a bigger party" if he was chosen in a speech which concluded with him vowing to support FIFA’s first new president since 1998.
"I am prepared to serve under the next president," he added.
He then expressed a wish for the future of FIFA.
"One day I hope the president will be a woman. I believe in unity, the Mandela way," he said.
He had earlier pointedly referred to the controversy surrounding the awards of the 2018 World Cup to Russia and 2022 tournament to Qatar.
He said: "I don’t think two World Cups should be awarded at the same time. That’s what brought us here."