Rolston blasted a slap shot through Calgary goalie Miikka Kiprusoff's legs to give the Wild the lead for the first time in the game.
Pavol Demitra, who also had an assist in the game, added an insurance marker and the Wild then held on to win its sixth straight game.
With the victory the Wild (42-25-7) pulled one point ahead of Vancouver for top spot in the NHL's Northwest Division, although the Canucks were still in action against the Detroit Red Wings when the Minnesota-Calgary game ended.
Marian Gaborik and Stephane Veilleux also scored for the Wild, while netminder Niklas Backstrom made 19 saves to improve his record to 18-8-5.
Despite the setback, the Flames (37-25-10) still hold onto eighth spot in the Western Conference standings.
Damond Langkow and Alex Tanguay counted goals for the Flames, who have now lost three straight after winning six of their previous eight contests.
It took Calgary just 32 seconds to strike first as a harmless-looking shot by Langkow handcuffed Backstrom and found the back of the net.
The Wild didn't get their first shot of the game until the 6:25 mark of the opening frame when Kiprusoff made a pad save on a breakaway attempt by Rolston.
Later in the period, Kiprusoff made another great pad save on Rolston to keep the Wild off the scoresheet. With Flames captain Jarome Iginla in the penalty box for hooking, Gaborik converted a nifty return pass in front of the net from Demitra to tie the contest at 1-1 before the end of the first.
Early in the second, Matthew Lombardi used his speed to cut around Minnesota defenceman Martin Skoula and centred a pass to Tanguay, who quickly snapped a shot past Backstrom.
Mid-way through the second Veilleux tipped a point shot by Minnesota blue-liner Keith Carney through Kiprusoff's legs and into the net to tie the game once again.
Minnesota had a great chance to go up one when Rolston feathered a perfect cross-ice feed to Pierre-Marc Bouchard, but Kiprusoff slid across to block the one-timer off of Bouchard's stick.
The Flames had a great chance late in the game to tie, but Backstrom made a nice save to turn aside a shot that was redirected by Calgary forward David Moss.
Demitra counted the insurance marker to round out the scoring.
Notes: - With the win, Minnesota ended a seven-game losing streak at the Pengrowth Saddledome. The Flames have only lost three times to the Wild in their past 18 home games. ... By setting up Langkow's first period goal, Iginla tied Kent Nilsson for sixth spot at 333 on the Flames all-time list for assists. He needs just four more helpers to pass both Paul Reinhart and Guy Chouinard and jump into fourth spot on the list.