The home side were on the back foot for most of their Premier Division clash against Alrewas at Queen's Park. But they rallied to set up an exciting finish before eventually losing by 19 runs.
Chesterfield, back in the top flight after winning Division One last season, made a good start as they attempted to chase down Alrewas' total of 238-8 off 50 overs. But they found it tricky attempting to force the pace against the visitors' four-strong spin attack, who extracted turn and bounce from a good wicket.
Will Smedley struck a vital blow when overseas star Kemira Wijenayake went down the wicket against him, was beaten in the flight and stumped smartly by Stephen Cole.
That reduced Chesterfield to 112-5 in the 28th over and they were also behind the clock. However, vice-captain Jordan Lemon and Eddy Allcock gave the hosts renewed hope with a stand of 86 in 19 overs.
They played themselves in carefully before Lemon, in particular, unleashed a volley of strokes all round the ground. However, there was always the suspicion that the asking rate would prove too much in the closing stages as the four spinners bowled 31 overs in succession for combined figures of 4-122.
Opening bowler Craig Swinfield returned to bowl Allcock for 28 but Lemon hit a straight six and another maximum over square leg to keep alive Chesterfield's hopes.
Ben Lodge added a couple of powerful blows to the boundary before being run out but his dismissal left the hosts needing a highly unlikely 23 off seven balls. Lemon was caught behind for 70 two balls later and Chesterfield were eventually bowled out for 219.
Earlier Alrewas, put in to bat, made a flying start before a fine catch by Luke Westwell in the gully ended an opening stand of 58 in 10 overs.
Chesterfield were never really able to pull back the advantage Alrewas gained in that first phase. Spinners Wijenayake and Harry Wilmott bowled well and Muhammad Zaroob took three wickets in a fine second spell. But Cole hit 53 to guide the visitors to a total that proved just enough.
Chesterfield seconds lost by six runs at Shipley Hall in Division Three North.
Skipper Adam Woodhouse took 3-42 as the home side scored 221-8 off 45 overs. In reply, Michael Michailidis raced to 74 off 62 deliveries but Chesterfield were bowled out for 215, losing their last two wickets to successive balls.
The third team won by seven wickets at Pilsley & Clay Cross seconds in Division Nine North. Timothy Imran took 3-31 to help bowl out the home side for 125 before Jamie O'Connor led Chesterfield home with 45 not out.
On Saturday Chesterfield travel to Belper Meadows, the seconds host Hundall at Queen's Park and the third team are away against Cutthorpe fourths.
On Sunday Chesterfield go to Nottinghamshire to play Attenborough in the Rothesay National Club Championship.