Chelsea paid the price for finishing in second place in their Champions League group after they were drawn to play Barcelona in the round of 16.
Barkley, who completed a £15m move from Everton to Chelsea on Friday, is eligible to play in the competition having not featured this season because of a hamstring injury.
And despite Barcelona's current fine form in La Liga - they sit top of the table by six points - the midfielder believes that Chelsea can see off the Catalan giants when the Champions League last-16 ties are played in February and March.
"We've got a tough game against Barcelona but, as you've seen in the past, Chelsea Football Club can beat Barcelona," Barkley told Chelsea TV.
"We've done that.
"I'm looking forward to it. It's been a dream of mine to play in the Champions League so I'm looking forward to getting started."