Jose Mourinho's side edged past Paris Saint-Germain on away goals on Tuesday night and are the outsiders to win the competition ahead of Friday's semi-final draw in Nyon.
Smith believes Chelsea's strong defence gives them a chance of lifting the trophy in Lisbon on May 24, but he believes Bayern Munich and Real Madrid are the outstanding contenders for the title.
And he told the Sky Sports Champions League Podcast Mourinho would prefer a meeting with current Spanish league leaders Atletico in the last four.
When asked who Chelsea want to avoid, the Sky Sports pundit replied: "Bayern number one, closely followed by Real Madrid you would imagine.
"We didn't think Chelsea had enough a couple of years ago and they ended up winning it. They've still got a very strong defence and arguably the best one.
"You're going to go a long way to beat that central defensive partnership of John Terry and Gary Cahill - plus Ivanovic, Azpilicueta and a very good goalkeeper, all marshalled by a very tactically astute manager.
Chelsea through to semi-finals
"If they defend well they could be a tough nut to crack and having got past PSG the other night they might start to believe their name is on the trophy again.
"But Real Madrid v Bayern Munich would be some final. I think, for me, they are the two best teams in the competition and you would want to see those two coming together.
"But you're at the mercy of the draw."
However, Smith says a match with Atletico, who knocked out Barcelona on Wednesday night, would not be an easy game.
And he believes Diego Simeone's team have a good chance of winning the Champions League for the first time ever.
"We are all looking at them as potential dark horses in this competition," he added.
"Diego Simeone is clearly a strong manager and it's a disciplined outfit; not the most expansive, free-flowing team but they have a very good defensive record and can squeeze by on one-nils.
"They could win La Liga. They have played five games against Barcelona they have not lost one; they've drawn four and won the last one.
"If Bayern draw Real Madrid in the semi and Real were to sneak through and Atletico were to beat Chelsea, all of a sudden you've got a shock on your hands there."
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