The Spanish giants are one of six teams Arsene Wenger's group runners-up could face, alongside Paris St Germain, Malaga, Borussia Dortmund, Juventus and Bayern Munich.
Song swapped the Emirates Stadium for the Nou Camp when he joined the Arsenal exodus during the summer and expects only one outcome if they meet for a place in the quarter-finals.
"Of course I would like to play against Arsenal. For me to go back there, where I had seven magnificent years, would be something very special," the 25-year-old said.
"If we draw Arsenal I'd be happy to see the fans again and go back to the club, even though if we go there it will be to get the best result possible.
"Arsenal's a big club, but Barcelona's a level above because of the talent of the players there.
"That's no disrespect to Arsenal because they have talented players, but I think the Barcelona players are above them. I saw a lot of people come and a lot of people go at Arsenal."
Song's desire will not be shared by the Gunners, who will be desperate to avoid a team that has been hailed by some as the greatest of all time.
Having finished second in Group B, the possibilities facing Arsenal are alarming and Wenger will also be anxious to evade last year's beaten finalists Bayern Munich and Serie A leaders Juventus.
Manchester United are the second Barclays Premier League side to make it through to the knockout stages after defending champions Chelsea and Manchester City failed to progress.
Real Madrid may be trailing Primera Division leaders Barcelona by 13 points but they are still the team Sir Alex Ferguson will want to avoid most, knowing only Champions League glory can redeem Jose Mourinho.
Porto, AC Milan, Shakhtar Donetsk, Valencia and Celtic are the other possibilities, with the latter setting up a fascinating Battle of Britain contest.
Celtic defied all expectations to qualify as group runners-up behind Barcelona, in the process securing more points than any other Scottish team in the Champions League pool stages with 10.
Other than United, they could meet Malaga, Juventus, Bayern Munich, Borussia Dortmund, Schalke or PSG.
Barcelona are favourites to claim their fourth Champions League title since 2006, followed by Real and Bayern, and Chelsea interim manager Rafael Benitez expects one of the heavyweights to be crowned winners.
"Barcelona, Real Madrid, the English teams, Bayern Munich and Juventus are strong teams," said Benitez, winner of the competition with Liverpool in 2005.
"Obviously they're the big names and they'll be there again, it won't change too much.
"You can find a surprise in some seasons but because those teams are so strong, I don't see there being any surprises this year."
Chelsea are second favourites behind Atletico Madrid to win the Europa League, their reward for finishing third in their Champions League group.
They are joined in the round of 32 by Liverpool, Tottenham and Newcastle, although none of the Premier League rivals are able to face each other at this stage.
Atletico are a possibility for Chelsea and Liverpool, while big names such as Inter Milan, Napoli, Benfica and Ajax remain in the competition.
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