Spain, Belgium and Turkey all came through their first qualification game unscathed.
Villa on target as Spain make winning start
Spain, Belgium and Turkey all came through their first qualification game unscathed.
Group 5 is among the more difficult to call, with established European heavyweights mixed with sides capable of producing potential upsets.
However, the big three in the group were all able to celebrate safely negotiate their way to three points on Saturday.
Reigning European Champions Spain made hard work of a home contest with Bosnia-Herzegovina before emerging as 1-0 victors.
David Villa, top goal scorer at Euro 2008, grabbed the only goal of the game on 58 minutes to ensure new boss Vicente del Bosque got off to a winning start in competitive action.
Turkey were the surprise package at this summer's European Championship and will be hoping to feature in South Africa in two years' time.
They travelled to Armenia for their first game, collecting a 2-0 win against their near neighbours.
Middlesbrough striker Tuncay Sanli opened the scoring just after the hour-mark, before Semih Senturk secured the points with a second on 77 minutes.
The most entertaining game in the opening round of fixtures came in Belgium as Rene Vandereycken's men overcame Estonia 3-2.
Wesley Sonck gave the Belgians the lead on 39 minutes, only to see Sergei Zeniov level matters on 57 minutes.
Steven Dufour restored the home side's lead on 75 minutes, before Sonck grabbed his second of the game 11 minutes from time.
Andres Oper set up a nervous finish for the hosts when he reduced the deficit to one in injury-time, but Estonia were unable to find an equaliser.