Former champions France were given a favourable pairing as they travel to Ukraine for the first leg on November 15 while Greece will host Romania and Croatia play their first leg in Iceland.
The second round of the two-legged ties will be played on November 19.
Former World Cup semi-finalists Portugal and Sweden were the first two countries pulled out of the hat as Cristiano Ronaldo will defy Zlatan Ibrahimovic in what will be a battle of star-studded line-ups.
“We have been drawn against a team against whom we will be playing two complicated matches, two relatively balanced matches,” explained Portugal coach Paulo Bento.
“Besides having one of the best strikers in the world (Ibrahimovic), the quality of their team (Sweden), is their collective spirit.
“They finished second in a group that had one of the best European teams and potential winners Germany.
“However regardless of the opponent, we will be playing these two matches with the aim of playing at the World Cup,” continued Bento.
Ibrahimovic believes Sweden are the underdogs.
“Portugal are favourites, but they are going to be two fantastic matches,” said the Paris Saint Germain star.
“We’re playing against a good team with many good players. Play-off matches are like two finals, it’s completely different from group matches.
“I think we have to reduce our errors and the team who makes the most will miss the World Cup.”
Didier Deschamps’ French side, who were narrowly beaten to top spot in their pool by defending champions Spain, travel to the Euro 2012 co-hosts where they defeated Ukraine 2-0 in group play.
“We were not seeded and could have played Portugal or Croatia who have a long history, but Ukraine is not a simple draw either,” Deschamps told Eurosport tv.
“They are on a run of seven matches without defeat and they concede very few goals as well as a long trip over there,” he continued.
“It’s good to have the return leg at home but one team will qualify and the other will be staying home for the World Cup.” added the 1998 World Cup winning captain.
Ukraine’s key player Artem Fedetsky of Dnepropetrovsk believes in his side’s chances despite a tough draw.
“We’ve already been buried after the poor start in the qualifying campaign.
“However, we managed to come back and reach the play-off stage. After that every single match for us was like the final, like a do-or-die mission.
“Now we have serious experience of playing the most important matches. We are a cohesive team now and, I believe, we have a fair chance to go through,” he added.
Romania are bidding to return to the final stages for the first time since 1998 and will fancy their chances against goal-shy Greece, who were beaten to top spot in their pool by Bosnia-Herzegovina.
Greece coach Fernando Santos feels the 2004 European champions can fulfil their dream and called on their fans to get behind the team.
“No matter who the opponent, the level of all the teams are very strong. The Romanians are of great quality and dangerous and difficult opponents.
“I would have preferred the first match to be away, but again, it does not matter. The message I send to the Greek fans is to believe in this team, to support us, to fill the stadium to push the team and help us,” he concluded.
Finally, Iceland look to qualify for the first time in their history against a Croatia side coming off back to back defeats against Scotland and in the midst of a managerial change.
The four winners will qualify for the 2014 World Cup in Brazil from June 12 to July 13.
Nine teams have already qualified from Europe – Netherlands, Italy, Belgium, Germany, Switzerland, Spain, England, Russia and Bosnia.
The draw for the eight groups of four that will feature in the first round of the tournament will take place on December 6 in Bahia, Brazil.