Algeria, Cameroon, Ghana, Ivory Coast and Nigeria all participated at the 2010 finals and have advanced as group winners to the five playoff matches that will determine Africa's representatives for next year's tournament in Brazil.
Hosts South Africa were a sixth representative from the continent in 2010 but have been eliminated from the 2014 race.
Reigning African champions Nigeria and the top-ranked Ivory Coast start as overwhelming favourites but the others need to get through testing contests if they are to repeat their qualification of four years ago.
Nigeria play away against Ethiopia on Sunday in the first leg of their tie, with home advantage to follow in November.
The Ivorians meet fellow west Africans Senegal in a repeat of last year's African Nations Cup qualification playoff, which was never concluded after the second leg in Dakar was abandoned following a stadium riot when Senegal fell behind.
The two protagonists clash again in Abidjan on Saturday and will play their second leg tie in neutral Morocco next month due to a ban on Senegal's home stadium.
The series of playoff matches begins in Ouagadougou on Saturday when Burkina Faso seek to crown a year beyond their wildest expectations with a good home result against Algeria.
Burkina Faso were surprise runners-up at the Nations Cup finals in South Africa at the start of the year and have since staged a miraculous comeback in the World Cup qualifiers after being docked points in the preliminaries for using an ineligible player.
Cameroon, who are boosted by the return of Samuel Eto'o after he threatened to retire, but were a far from convincing group winner, take on Tunisia in their two-legged tie, starting in Tunis on Sunday.
Tunisia only made it to the playoffs when Cape Verde were stripped of an away win in Tunis last month because they fielded a suspended player.
The Tunisians have a new coach in charge for their second chance after former Netherlands captain Ruud Krol agreed a two-month contract in September.
Krol played in two World Cup finals and says he has told his new charges they are on the brink of a career-defining moment.
"The World Cup puts all other trophies in its shadow, the whole world is watching and the Tunisians must realise they have a tremendous chance now to qualify," he told reporters this week.
Ghana host Egypt in the most eagerly anticipated of the five playoff ties, with the first leg in Kumasi on Tuesday.
Ghana have already ratcheted up the pre-match temperature by asking FIFA to move the Nov. 19 return game from Cairo because of the fraught political situation in Egypt.
It is the first time since 1989 that playoffs have been used to determine Africa's World Cup representatives.