Former Miller Abdulai Bell-Baggie blasted in from close range in stoppage time at the end of extra time to leave Spireites without a League Cup win since 2006.
In the first game at the renamed Proact Stadium, Cole Stockton put Rovers ahead early in added time, his first goal in his first senior start.
Jack Lester levelled with a fine finish but Rovers hit back to finish things off, though Lester was within a whisker of a second equaliser with the game’s last action.
Rovers, hit by injury and International call-ups, fielded 19 year old Ben Gibson in the heart of their defence having signed him on loan from Middlesbrough earlier in the day. Owls’ loanee Liam Palmer made his Rovers debut.
Sam Togwell forced the first decent save with a 15 yard half-volley but Rovers came close when Robinson crossed for Jean-Louis Akpa-Akpro to hit the bar with a header.
Palmer should’ve opened the scoring. He caught Sam Hird in possession but flicked his shot wide.
The second half started at a pace. Trotman had a header blocked on the line and moments later Terrell Forbes had to be alert to head a Rovers attack clear and Tommy Lee had to gather a downward header from Stockton, who soon after saw Lee’s fingertips keep an angled effort out. James Wallace headed wide and Stockton hammered against the post as Rovers looked the more likely scorers. However the home fans came to life when Lester came off the bench, Talbot, Whitaker and Jordan Bowery, three times, drilled in efforts within minutes of his introduction.
Hird limped off, a worrying sign, ahead of man of the match Robinson firing within inches and then at Lee, who gathered well. Talbot had an angled shot deflected wide towards the end of normal time, which ended with the hosts attacking, though fortunate to still be in the tie.
Chesterfield: Lee 7; Forbes 7, Hird 6 (Darikwa 76, 6), Trotman 6, Smith 8; Talbot 7, Allott 7, Togwell 6, Whitaker 7; Richards 6 (Lester 67, 7), Westcarr 6 (Bowery 55, 6). Subs (not used): O’Donnell, Boden, Randall, Clay.
Rovers: fon Williams 6; Holmes 6, Kay 6, Gibson 7, Bakayogo 7; Thompson 7, Palmer 6 (Harrison 111), Wallace 7, Robinson 9 (Power 111); Akpa Akpro 6 (Bell-Baggie 100), Stockton 8. Subs (not used): Mooney, Vaulks, Kirby.
Goals: Stockton 93, Lester 108, Bell-Baggie 120+2
Bookings: Trotman, Hird, Togwell, Whitaker (Chesterfield), Bakayogo, Wallace (Tranmere)
Ref: David Webb (Durham)