But moments later, Nenad Milijas beat goalkeeper Joe Hart with a low, 20-yard drive to put Wolves level.
Ana Ivanovic, a former No. 1 from Serbia, will team with Nenad Zimonjic, one of the world's best doubles players.
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They struck after only three minutes when Kevin Doyle got the faintest of headers on a cross from Nenad Milijas.
"Nenad is a star player and an international of note in a talented Serbian team, " Wolves chief executive Jez Moxey told the club's website.
Last year's champs, Daniel Nestor and Nenad Zimonjic, split after the tournament and have been playing at this year's tour finals with new partners.
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Spanish midfielder Alberto Zapater netted a free-kick after just four minutes and Giuseppe Sculli doubled the lead on 39 as he volleyed in a cross from Nenad Tomovic.
Midway through the half, Wolves substitute Nenad Milijas cut inside from right and unleashed a low left-footed shot which brushed Richard Kingson's fingertips before smashing into the upright.
The tournament began with a surprise in the doubles when defending champions and top seeds Daniel Nestor and Nenad Zimonjic lost to Polish eighth seeds Mariusz Fyrstenberg and Marcin Matkowski.
The 2010 champions reached the last eight on Saturday when Viktor Troicki and Nenad Zimonjic defeated Belgian pair Steve Darcis and Ruben Bemelmans in four sets 6-4 6-4 5-7 6-4.
Nenad Milijas had a long range free-kick pushed aside by Jussi Jaaskelainen, who also stood up bravely to deny Matt Jarvis and tipped a well-struck 25-yard effort from Milijas around the post.
Radek Stepanek and Tomas Berdych defeated Nenad Zimonjic and Ilija Bozoljac 6-4 6-2 7-6 (7-4) in a match which lasted two hours and 23 minutes on the clay at the O2 Arena.
Johan Brunstrom and Robert Lindstedt ensured the Swede's took the tie into Sunday with a gruelling 3-6, 6-3, 7-6 (7-4), 6-7 (3-7), 10-8 win over Janko Tipsarevic and Nenad Zimonjic after Serbia had won both of Friday's opening singles matches.
The fourth-placed home side -- at that point 2-1 down and playing with 10 men since before halftime after Nenad Tomovic was sent off for elbowing Balotelli's strike partner Stephan El Shaarawy -- fought back to equalize through a late penalty by David Pizarro.
Didier Drogba's excellent finish from Yuri Zhirkov's cross put Chelsea ahead and they seemed on course to end the first phase of their assault on the Champions League with a victory until Apoel substitute Nenad Mirosavljevic raced clear to equalise with three minutes left.
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