The Brewers stole a nerve-jangglingly late 2-1 Proact Stadium win after the visitors equalised Sam Hird's early goal and then scored in the very final minute of added on time
An early Hird header in the second minute calmed home nerves as he stole in front if the 'keeper to force the ball home right from the off for the hosts.
Just as early in the second half Brewers' striker Scott Beavon made things level as he tapped home after an initial visiting shot had been blocked.
The game seemed set for a draw buut after the referee had not given what appeared a clear Spireites penalty for a foul on Jay O'Shea the Brewers broke and sbstitute Jerome Binnom-Williams slotted home to win the game.
Dean Saunders made two changes to his side following last week's 1-0 away defeat at Coventry City, with Lee Novak missing out through injury, and Chris Herd dropping to the bench, with Gboly Ariyibi and Drew Talbot coming into the side. Mani Dieseruvwe missed out through suspension after his red card last time out.
The Spireites came out of the blocks quickest and got straight at their oppontents, with Ariyibi winning a corner on the right after some good work from the winger, a set piece which led to the opening goal.
Dan Gardner took the corner which was met by the head of Hird, who headed into an empty net after veteran keeper Jon McLauglin failed to claim the ball.
It was a strong start by Chesterfield, but they were almost pegged back by the Brewers through Nasser El-Khayati. After a jinking run beating two Spireites players in the area he saw his low goal-bound shot cleared off the line by Ian Evatt.
Burton came again shortly after, this time through the lively Lucas Akins. He beat the offside trap despite a few Chesterfield eyebrows being raised, before making a hash of his effort, dragging a low shot wide of Tommy Lee's goal.
El-Khayati looked dangerous all game, and was soon close to levelling to scoreline again. Duffy again played him in, but his goal-bound shot was this time blocked by his own man Beavon.
The game soon became a tight and scrappy affair, with neither side able to keep the ball in possession. However, Gardner broke with pace down the left delivering the perfect ball for Ariyibi at the back post. His downward header went just wide, but got the crowd back on their feet.
The Brewers then sprang back into life, gaining a foot-hold in the contest. Beavon was again played in behind the Spireites defence, he pulled it back for Akins, but the former Stevenage striker saw his dangerous effort blocked by the impressive Hird in the last real chance before half time.
The second half had barely begun before Beavon found an equaliser for the visitors. Calum Butcher found El-Khayati in the area. His shot was blocked by Evatt, but the rebound fell kindly for Beavon, who slid the ball under Lee from a tight angle just one yard out.
Burton then had the chance to go in front seconds later, again through Akins. Former Spireites loanee Mark Duffy ran clear down the left and squared the ball to him, but his shot was wild and ended up high in the end housing the visiting fans.
Akins then had a chance to redeem himself after El-Khayati did well to work an opening in a congested penalty area, however Akins' shot came back off the underside of the bar.
The game opened up from there, with Burton looking like a side that deserved to be top of the table. Beavon saw another shot blocked by Evatt, while at the other end Hird forced an excellent save from McLaughlin. His header was caught by the experienced keeper to deny the Spireites a goal that would have swung the match in their favour.
Rai Simons then came on for his debut for the Spireites, having scored three times in two games for the reserves. He immediately began to influence the game, breaking through the Burton midfield and finding fellow sub Armand Gnandulliet who fired wide.
The pair soon combined well again. Simons won a free kick after a fantastic run on the left, O'Shea's delivery to the back post was headed low at goal by Gnandulliet, but saw the ball cleared off the line when a goal looked certain.
The game was set for a frantic finish after seeing a host of chances going begging in the second period, and it didn't disappoint. Substitute Jerome Binnom-Williams drove forward for the visitors and played in El-Khayati, but his effort was well saved by Lee.
At the other end, Dan Jones' dangerous cross was flicked agonisingly wide by Gnandulliet with McLaughlin beaten.
Defender Damien McCrory had a chance to win it in added time. El-Khayati held the ball up inside the Spireites box and picked the perfect ball to McCrory, but his volley was well blocked by man of the match Hird.
The Spireites were then denied what looked like a penalty when O'Shea was felled just inside the area, much to the dismay of Dean Saunders, before Burton scored the winner on the break.
Binnom-Williams was played in on the halfway line by El-Khayati, before firing a cool finish beyond Lee to delight the away fans and condemn the Spireites to a second successive defeat.
Chesterfield: Lee (gk) - Jones, Evatt, Hird, Talbot - Morsy (c), O'Neil, Ariyibi, O'Shea, Gardner (Simons 66')- Ebanks-Blake (Gnanduillet 71')
Subs not used: Cairns (gk), Banks, Raglan, Herd, Orrell
Burton Albion: McLaughlin (gk) - Edwards, Mousinho (c), Weir, Beavon, Akins (Palmer 89'), El-Khayati, Butcher, McCrory, O'Connor, Duffy (Binnom-Williams 84')
Subs not used: Matthews (gk), Joachim, Naylor, Thiele, Flanagan
Chesterfield: Hird 2'
Burton Albion: Beavon 46', Binnom-Williams 90'
Attendance: 6,752 (915 away fans)