The Steelmen were drawn against Russian side Kuban Krasnodar in Friday's third qualifying round draw.
Hoping to join them at that stage in qualifying are fellow Scots Saints, who claimed an impressive 1-0 first leg lead over Rosenborg in Norway on Thursday night.
Motherwell face a tough challenge themselves against a side who finished fifth last season and who have been boosted by the arrival of former Liverpool and QPR striker Djibril Cisse this summer.
McCall said: "It was fantastic last night, St Johnstone with a positive attitude and getting a great result. That's what we're going to have to have.
"First and foremost we have to go over to Russia and make sure we are still in the tie but hopefully with a lead.
"We've got to aim to progress into the next round. We will just be positive and do the best we possibly can.
"If we can do our best and it gets us through then all well and good."
McCall's knowledge of Kuban Krasnodar may be limited just now but the Fir Park boss expects to be fully up to speed on them by the time they meet.
He said: "To be fair to the media team and our chief scout Bobby Jenks, I just came back from training and there were two dossiers on my table.
"We obviously don't know a lot about them and they probably know even less about Motherwell.
"They finished fifth last season and they signed the boy Cisse so we know bits and bobs.
"They play Zenit (St Petersburg) next Friday and we are all clamouring to see which one of the coaching staff will go to that because it's supposed to be a nice place.
"I think Bobby will go over and watch them and we will do our homework the best we can."
Motherwell finished second in the Scottish Premier League last season and will be hoping for a repeat this time.
McCall knows an extended European run could have a detrimental impact on domestic results but it's a chance he would gladly take.
He said: "I'm sure it would [impact on results] but we would take it right now.
"You can never be grateful that you're out of the tournament.
"I was speaking to Alan Pardew about it, Newcastle played a lot on the Thursday and the league form certainly suffered - and they've got a big, big squad.
"That would be a concern but one I would happily accept if it meant going into forbidden territory."