The Scots - with McCall as part of the coaching set-up - pulled off a major shock when they defeated top seeds Croatia in a World Cup qualifier in Zagreb last month.
Motherwell were dumped from the Champions League qualifiers by Panathinaikos last year before suffering an early exit in Europa League qualification at the hands of Levante.
McCall knows the odds are likely to be stacked against his side when they find out who they will face in the third qualifying round of the Europa League in Friday's draw in Nyon but he hopes to fare better this time.
He said: "We are looking forward to the draw. It will be a big ask but we will have a real go at it again and see if we can progress. The smaller [Scottish] clubs haven't done as well in Europe.
"In the last few years, we haven't got as far as we would have liked so hopefully we can do it this time.
"We will be underdogs in most games because the opposition we will be up against will be better but it doesn't mean to say we can't pull off a shock. Everybody remembers Scotland's last game."
Motherwell will be boosted in the season ahead by the capture of defender Stephen McManus, who signed a one-year-deal with the Fir Park side after also training with Hibernian.
McCall said: "When he went to Hibs for a week's training, I was holding my breath if I'm honest, but thankfully he decided to come here.
"He is another proven player, he's SPL quality, he's a good leader and has caps for Scotland. He's a really good addition for us. To be honest, I wasn't looking for another centre-back.
"Simon Ramsden did well there for us last year and we've lost two full-backs but when a player of Mick's pedigree and quality and leadership comes up, I thought we'd have a little sniff and we are delighted to get him."
McManus has not featured for Scotland since 2010 but McCall believes he still has the qualities needed to win himself a recall if he impresses at Motherwell.
He said: "I don't see why not. I know he's got a good relationship with Gordon Strachan.
"It depends on himself and how well he plays. Scotland have probably struggled at centre-back in recent seasons. It will be down to Mick and, if he plays as well as he can, then there is no reason why not."