The two sides will meet in the first leg of their semi-final clash at Stamford Bridge next week, before colliding again at Camp Nou on April 24.
The Blues were denied a place in the 2009 tournament decider by a last-minute goal from Andres Iniesta, but Scolari is expecting Barca to breeze past the English outfit this time around.
"Barcelona has a 90 per cent chance in the Champions League tie against Chelsea," the Brazilian told COM Radio. "Barcelona are the favourites. But then the favourites still have to win on the field."
Scolari, though, feels that the other semi-final showdown, between Bayern Munich and Real Madrid, is almost too close to call.
"The Madrid-Bayern tie is very even," the World Cup-winning coach mused. "I think the game in Munich will decide who gets knocked out.
"If Madrid get a good result, they will be in the final. If Bayern wins by two goals, it will be difficult for Madrid."
Turning his attention to the increasingly fascinating battle between Barca and Madrid for the Liga title, Scolari opined that the momentum has now swung in favour of the Blaugrana, who have closed to within a point of Los Blancos over the past month.
"The 10-point advantage that has now been cut by Barcelona is becoming an emotional problem for the players of Madrid," he said.
"I think the mental side of things is changing in favour of Barcelona and they now have the conditions to be champions.
"If Barcelona beat Madrid [in the Clasico later this month], they have a good chance of being crowned champions.
"But if Madrid win or draw, they will go on to win the title."
Scolari, who led Brazil to World Cup glory in 2002, is currently in charge of Palmeiras.
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