Former world champions France will play Ukraine next month for a place at Brazil 2014 while Portugal meet Sweden in a playoff featuring two of football's most exciting players, Cristiano Ronaldo and Zlatan Ibrahimovic.
Rank outsiders Iceland, who will be one of the smallest countries to ever reach the finals if they qualify for Brazil, are up against Croatia while Greece take on Romania after the draw was made for the four European playoffs at FIFA headquarters on Monday.
France, who were unhappy to miss out on a seeding in the draw and at world number 21 are ranked one place below Ukraine, boast an unbeaten record against the East Europeans with four wins and three draws.
"Ukraine are a team who do not concede a lot of goals but it's good we are playing the second leg at home," said French coach Didier Deschamps, who was relieved to avoid Portugal.
France, winners of the trophy in 1998, finished second to world champions Spain in Group I qualifying while Ukraine were runners-up to England in Group H.
The last meeting between France and Ukraine ended in a 2-0 win for Les Bleus after thunder and lightning caused their Euro 2012 match in Donetsk to be briefly suspended.
Sweden coach Erik Hamren said he hoped his team, led by Ibrahimovic, would catch 1966 and 2006 semi-finalists Portugal on an off day.
Highs and lows
"Portugal, when they are at their highest level, are a world class team, you saw that in Euro 2012, but sometimes they are a little like this and we hope they will be like this," Hamren told reporters as he lowered his hand.
"(Ibrahimovic) has been really good for us for a long time now, he is the match winner for us, a world class player, and they have one too.
"That's interesting because you can have tactics and scouting but a world class player like Ronaldo or Ibra can change a game and do something extra."
Portugal, who finished second to Russia in Group F and were the highest-ranked team in the draw at number 14 on the list of football's ruling body FIFA, take on Sweden at the 66,000-capacity Luz stadium in Lisbon in the first leg on November 15.
The two have met 15 times with Sweden winning on six occasions and Portugal three but the Scandinavians have not beaten their playoff rivals in seven matches since 1984.
The sides met twice in the qualifiers for the 2010 World Cup and drew both matches 0-0.
"Sweden are a team who will give us two very evenly-balanced games. Although they have one of the best forwards in the world, Sweden are strong collectively," said Portugal coach Paulo Bento.
Iceland, who have a population of about 320,000 and have never qualified for a major tournament, have already exceeded expectations by finishing ahead of Slovenia and Norway in their group.
The lowest-ranked team in the draw at number 46, Iceland's only previous meetings with their playoff opponents came in 2005 when Croatia won at home and away in the qualifying stages for the 2006 World Cup in Germany.
"I think Croatia is okay," said Iceland boss Lars Lagerback.
"The advantage is I know the new coach (Niko Kovac) a little bit and I also had experience against Croatia when I was coaching the Swedish team so I know what we can expect.
"We have a pretty good team so, even if we're not the favourites, look out for Iceland."
Kovac said: "We are very happy with the draw especially because we will be at home in the return leg in Zagreb (on November 19).
"But it would be audacious to take anything for granted because Iceland are a young and ambitious team whose coach has World Cup experience with Sweden and Nigeria.
"He once lectured me at a coaching academy, now we will come face to face as rivals."
Greece, who finished second to Bosnia on goal difference in Group G, first met Romania in 1930 and will be wary of a team that beat them 3-1 in a friendly the last time they clashed in 2011.
"I can tell you I am not satisfied, I wanted another team," said Romania coach Victor Piturca.
"Greece are strong opponents. They're a well-organised team."