Blues have reached five semis - and one final - in the past six years, and Hiddink said: "These players don't have five, six or seven more years to have the same chances they have had in recent years.
"It's very respectable that Chelsea made it to five semi-final in the past six years - it is a sign of big ambition.
"But this is the last occasion for these players to be where they want to be.
"They have a lot of desire to win the Champions League. We must play with intelligence and emotion - if we combine both we have a very good chance."
Following the goalless draw in Spain last week, Barcelona have been critical of Chelsea's tactics, accusing them of playing negatively and behaving over aggressively.
They then disposed of Spanish championship rivals Real Madrid with ease, winning 6-2 at the Bernabeu over the weekend.
As a result, motivation within the Barca camp is now at a high, but Hiddink watched the La Liga encounter and is confident he will keep Lionel Messi, Thierry Henry and Samuel Eto'o at bay