The Fir Park side moved level with Inverness in second place in the SPL after a ruthless attacking display. Tom Hateley headed home Jamie Murphy's cross after 10 minutes to give the hosts the lead against the run of play.
Motherwell punished Aberdeen's failure to take their chances as Murphy doubled their advantage on the half-hour mark, however Jonny Hayes powered through the midfield before steering an effort past Darren Randolph to reduce the deficit just minutes later.
Murphy notched his 10th goal of the season on the stroke of half-time to provide a timely boost for the Fir Park side and Michael Higdon added a fourth 10 minutes into the second half.
"I'm really pleased and delighted for the fans, as a lot of people talk about our poor home results," McCall said.
"We managed to take our chances today and could have taken more - I thought today when we got ahead we played some really good football. As a manager it's a delight to win games, but if you can do it like that then all the better."
McCall made two changes to his side for the visit of the Dons, with Zaine Francis-Angol and Fraser Kerr replacing Chris Humphrey and Steven Hammell.
After losing 2-1 to Aberdeen at Fir Park in the fourth round of the William Hill Scottish Cup, McCall felt he had to make some necessary adjustments to change the outcome of the match this time round.
"I decided to match them and play three forwards up against their three centre-backs and I think with Murphy's two goals, one for Higgy (Higdon) and Henrik (Ojamaa)'s performance too it worked," added McCall.
"It can be a dangerous game, but you have to have faith in your defenders and that your frontmen can do more damage to them than they can to you. If there were any scouts here today they probably went away with five or six names on a piece of paper."