Ramnaresh Sarwan and Chris Gayle became available to play for the West Indies when they cancelled personal sponsorship contracts on Wednesday.
But their decision came too late to enable them to be selected in the first Test against South Africa, which starts in Georgetown on Thursday.
"Sarwan and Gayle have cancelled their contracts with Cable & Wireless, which means they will be eligible for selection again," the chief executive of the West Indies Cricket Board, Roger Brathwaite, told Reuters.
The players made their decision less than 12 hours before the first ball was scheduled to be bowled in the first Test.
"They will not play in the match, we will pick the team from the current squad," Brathwaite said.
Sarwan and Gayle were part of a group of seven players, including regular West Indies captain Brian Lara, who were unavailable for selection because of a potential dispute between the West Indies' main sponsor, Digicell, and the players' personal contracts with Cable & Wireless.
The seven were Lara, Sarwan, Gayle, Dwayne Smith, Dwayne Bravo, Ravi Rampaul and Fidel Edwards.
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He added: "We are in constant discussion with the players' association and we sent off another proposal to them today. Hopefully we will receive a positive response."
West Indies media liaison officer Imran Khan told Reuters: "The situation is that we will go into the first Test with the current 13-man squad, but that squad was chosen for the first Test only."
West Indies coach Bennett King painted his team as the underdogs going into the four-Test series.
"South Africa play a very tough style of cricket and it is one we can learn from," said King. "We hope a few diamonds will emerge from the coal."
Shivnarine Chanderpaul, who will captain the West Indies in Lara's absence, said: "We've been working hard at our camp in Barbados and the guys are prepared for the series."
South African captain Graeme Smith said his team had come to the Caribbean with a point to prove after their first loss to England in a home Test series in 40 years this season.
The visitors are without stalwart fast bowler Shaun Pollock, who has remained in Durban for treatment to an inflamed ankle.