Tendayi Darikwa got the scoring underway after seven minutes, with Sam Hird doubling the lead before half time. Villa pulled one back just after the break through Jack Grealish before Sam Morsy capped a terrific week for him and his team with a decisive third near the end.
It only took 90-seconds for the hosts to show they were up for occasion, when Armand Gnanduillet laid the ball off to Gary Roberts, whose picked strike was saved by a sprawling Brad Guzan in the Villa goal.
After seven minutes the Spireites' bright start was converted into goal. A through ball was poked forwards with right-back Darikwa springing onto the ball and sliding a shot just below the onrushing 'keeper to open the scoring.
Nine minutes in and the hosts were within a whisker of a second. Roberts' corner was headed goalwards by Sam Hird, parried by Guzan, and Ritchie Humphreys was there to prod in a shot that was somehow blocked on the line.
The visitor's Joe Bennett curled a freekick just wide of Tommy Lee's upright with Villa's first effot of the game 15 minutes in. Callum Robinson then shot high and wide 20-yards from goal.
The Spireites were still carrying a threat going forwards and came close when some Roberts trickery on the right wing produced a cross that Gnanduillet headed back and Humphreys, enjoying his role further up the pitch, was close to connecting with. Moments later, Gnanduillet forced a save from Guzan with a powerful header that Evatt followed up with a shot over the bar.
Approaching the half hour mark, the visitors came their closest yet and hit the woodwork. Graham Burke collected the ball on the edge of the box and drove a rising shot that beat Lee but came back off the underside of the crossbar.
With the interval approaching left back Daniel Jones showed wonderful pace to beat two men down the wing, his cross matched the his run and Gnanduillet forced Guzan into a save from the highest of drawers.
The resulting corner resulted in the second of the game for the Spireites. The ball swung its way to Hird who met the ball firmly with a downward header, the ball going in via a slight deflection off Ritchie Humphreys.
Less than a minute into the second period and Chesterfield came close to a third when Romy Boco shot from 12-yards, but his effort was too close to the 'keeper.
Having made six changes at half time Villa were showing themselves as more of an attacking force and pulled a goal back after 50 minutes. Charles N'Zogbia got himself to byline and pulled a low ball back to fellow substitute Jack Grealish who found the target via the far post.
The next incident came from the sideline, with Spireites defender Liam Cooper, the subject of transfer speculation all day, came on to replace Humphreys. However, it was his central defensive partner Ian Evatt who next went close, heading a yard over the bar.
The hosts were continuing to give as good as they were getting, substitute Jay O'Shea close to finding the head of Gnanduillet with a swirling centre.
N'Zogbia again showed his class after 72 minutes, cutting inside and firing in a shot that cleared the bar.
With ten minutes left on the clock Chesterfield showed they still had plenty left in the tank as a tricky run from Dan Gardner found Jimmy Ryan who lofted up a delicate cross that was just a defender's flick away from finding the head of Eoin Doyle. Moments later, Ryan fired a shot in from the edge of the box that grazed the side netting.
Villa's livliest player Callum Robinson was first onto a ball over the top as the Villans looked to level, but Darikwa showed pace and precision to track back and nick the ball away just as Robinson was looking to strike.
However, with six minutes remaining, the Spireites had their definitive third. Doyle found space in the box, and laid the ball off to Morsy, who cut back past a defender home off the bar from near the penalty spot.
Late on some younger players entered proceedings, all part of a fine Spireites victory.
Chesterfield: Lee (gk) - Jones (Maguire 90'), Evatt (c) (Onovwigun 89'), Hird (Gardner 72'), Darikwa - Morsy (Clark 86'), Ryan (Dawes 86'), Humphreys (Cooper 54'), Roberts (Raglan 76'), Boco (O'Shea 54') - Gnanduillet (Doyle 72')
Subs not used: Wright (gk), Daly, Morrison, Broadhead
Aston Villa: Guzan (gk) - Lowton (Bacuna 45'), Herd (Okore 45'), Donacien, Bennett (Stevens 45') - Gardner (El Ahmadi 45'), Johnson, Carruthers, Burke (N'Zogbia 45') - Tonev (Grealish 45'), Robinson
Subs not used: Given (gk)
Chesterfield - Darikwa 7', Hird 43', Morsy 84'
Aston Villa - Grealish 50'