The Ghana-born 1998 World Cup winner, who won the Champions League with Marseille and AC Milan, also predicted Ivory Coast could be the surprise team and Argentina's Sergio Aguero the top scorer.
Argentina have the talent to win even if Barcelona's Lionel Messi does not play in every match, he told Laureus.com in an interview.
"I am sure collectively Argentina will be able, with Messi at top or without Messi at his best, to win the World Cup," said the Frenchman.
"Honestly I see Argentina playing without Messi," he continued. "Messi is not specially the key player of Argentina, you will see."
Desailly said champions Spain had the potential to defend the trophy, with fresh talent coming in to boost established players, but hosts Brazil could buckle under the burden of expectation.
"The first game will be very important but I'm sure confusion will be in the team." I'm sure it will be difficult for them to join altogether," said the 45-year-old. "Brazil will face a lot of problems for this World Cup."
The former Chelsea centre back saw "no expectation" for 1966 winners England.
"England do not have individual players who can make the difference," he declared.
"Obviously, people will talk about (Wayne) Rooney but in the previous World Cup he did not perform.
"It will depend on the collective play of the team, good young players who fit in and the cleverness of your coaches," Desailly added.
"Otherwise, England will not go to the final stages. I think even Belgium have a better potential to go to the final stage than England, on their individual capacity."
France are managed by 1998 World Cup-winning captain Didier Deschamps and Desailly said individual talent was certainly there.
"The only problem is collectively, France does not perform unless they are scared of getting eliminated," said Desailly.
"We are not expecting to win the World Cup. We are just there, hanging, hoping that game after game we can build up collective motivation."