The Red Devils are bracing themselves for two mouth-watering legs against bitter rivals Liverpool in UEFA's sister competition, with the first leg taking place at Anfield on Thursday.
It's the first time in history that the two clubs will lock horns in European competition and excitement levels have already reached boiling point before a ball has been kicked.
Smalling says United are doing plenty of work on the training ground with manager Louis van Gaal to ensure they won't get caught up in the occasion, but says even if they do, they can use that to their advantage.
"It's good that the manager sees it from a tactical viewpoint and we work on the training pitch before the game on our tactics so we don't get caught up in the occasion," said Smalling, who may captain United in Wayne Rooney's absence.
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"But when you cross over that white line, I think the emotion can drive you on and hopefully bring out a better performance.
"These are games the players look forward to and it's one I'm certainly looking forward to playing in."
Smalling also believes winning individual battles will be key to United enjoying success across the two legs.
"I think, quite often, the first 20 minutes can be quite frantic," said Smalling. "But you want to get the upper hand on your opponent, whoever you’re playing against.
"For me, it's the striker. Very early on, you want to get an early challenge in and make sure you dominate."