Scott Boden opened the scoring in the 31st minute but his strike was cancelled out by National League top-scorer Sam Barratt who netted twice to ensure all three points went back to Berkshire.
John Pemberton made three changes to his starting eleven. Joe Rowley made his first start of the season. Scott Boden featured for the first time since the opening day and Jordan Cropper returned to the side.
The visitors claimed the first chance of the game just a few minutes in when Ryan Upward watched his effort roll wide.
Chesterfield were presented with a great chance to take the lead when Laurence Maguire was denied by the woodwork in the 18th minute. The defender received the ball from Tom Denton who flicked on David Buchanan’s cross but Maguire saw his header from close range ricochet back at him off the bar.
Just over ten minutes later Boden gave Town the lead. Maidenhead failed to deal with Kyle Letheren’s goal kick and the ball found Boden who’s half-volley flew over the head of Taye Ashby-Hammond and home.
The visitors put John Pemberton’s men under pressure in the later stages of the first half. Firstly Manny Parry nodded wide from a corner before Upward’s chance was deflected away from goal.
The opening minutes of the second half saw both teams nearly find the back of the net.
First up, Boden missed the chance to double their lead when a weak Magpies’ clearance allowed him to pick up the ball inside the box and direct an effort on goal but United cleared off the line to keep the deficit at one.
At the other end Nathan Blissett nearly levelled. Maguire was the wrong side of the striker, allowing him to turn and get a shot away but Letheren did well to deny the number nine with his legs.
Alan Devonshire’s side got a leveller just before the hour mark when Barrat’s cross somehow evaded everyone and trickled into the net.
Chesterfield nearly found themselves in the lead again when Buchanan tried a belting volley which struck the inside of the post.
But it was Barratt who netted again. The in-form winger broke free from his marker and headed in Josh Coley’s corner to put the Magpies into the lead with twenty minutes to go.
A late chance fell to Jordan Cropper but he could only steer his effort into the side netting.
The away side claimed their fifth win on the spin whilst Chesterfield will look to bounce back on the road against Altrincham on Tuesday.
Chesterfield: Letheren, Cropper, Sharman (Rawson 78’), Evans, Maguire, Buchanan, Butterfield, Weston, Rowley (Kiwomya 90’), Boden, Denton
Unused subs: Wharton, Hollis, Smith
Maidenhead: Ashby-Hammond, Wells , Donnellan, Parry, Coley, Blissett, Sparkes, Ince, Upward, Massey, Barratt