The Lionesses were facing their first qualifying defeat since November 2002, but the Manchester City midfielder grabbed a late draw for her side by prodding home an Alex Scott cross in the 84th minute.
An uncharacteristic mistake by goalkeeper Karen Bardsley had gifted the visitors a first-half lead, but Mark Sampson’s side bounced back in the second half and were rewarded with a 1-1 scoreline.
It preserves England’s unbeaten start to their Group 7 campaign after wins over Estonia and Bosnia last year.
Belgium still top the table, but England are only a point further back with a game in hand.
Football was briefly forgotten about before kick-off as both teams mixed together in the centre circle for a period of silence to remember the victims of the terror attacks in Belgian capital Brussels last month.
The hosts saw more of the ball in the opening exchanges in what was England’s first match in Rotherham since their 1-0 win over Canada in 2013.
With just one change from the team that drew 0-0 with France last time out – Alex Greenwood in for the injured Claire Rafferty – Mark Sampson’s side registered two early chances, as Williams found Toni Duggan with a clever free-kick and the striker curled a shot just over the top.
Her Manchester City club mate, and strike partner against Belgium, Jill Scott then tried to lob Justien Odeurs following Greenwood’s corner but the keeper scrambled back to catch the ball on the line.
But with England looking comfortable, disaster struck.
Bardsley tried to deal with a long ball forward from the Belgium defence but missed her kick and Janice Cayman took advantage by rolling the loose ball into the empty net.
Mark Sampson and his squad will now travel to Bosnia & Herzegovina for their next Euro Qualifier
Somewhat rattled by their keeper’s rare error, England were only able to muster two real chances before the break, and they both came late on.
Williams tried to catch out Odeurs by curling a free-kick towards the near post but the keeper was equal to it and then Jill Scott headed a Greenwood set piece on to the roof of the net.
There was a flurry of shots midway through the second half as Greenwood, Cayman and Julie Biesmans all had efforts fairly comfortably saved.
Sampson made two changes in and around the hour mark, replacing Demi Stokes and Duggan with Karen Carney and Eniola Aluko respectively – and it was all England from that point onwards.
But the Lionesses weren’t the only ones making substitutions, as fourth official Jane Simms had to come on for injured assistant referee Brigittams Makkosnepetz.
Steph Houghton and co. piled on the pressure in the final quarter and had half-hearted appeals for a penalty turned down when Alex Scott tumbled in the box. The skipper then fizzed a shot just wide of the upright before Jill Scott’s rescue act.
Her namesake Alex, winner of Bear Grylls’ Mission Survive on ITV, delivered a delicious cross into the box which Carney headed goalwards. The ball was blocked by two Belgium defenders but Jill Scott was on hand to poke the loose ball into the back of the net.
There were two chances to win the game late on as Williams’ overhit cross was turned behind by Odeurs, who then saved Houghton’s free-kick.
But England will fly to Zenica at the weekend, where they will take on Bosnia & Herzegovina next Tuesday, buoyed by the maintenance of their unbeaten start to Euro qualifying.
England (4-4-2): 1 Karen Bardsley (Manchester City); 2 Alex Scott (Arsenal), 5 Steph Houghton (captain; Manchester City), 6 Casey Stoney (Arsenal), 3 Alex Greenwood (Liverpool); 7 Fara Williams (Arsenal), 4 Jordan Nobbs (Arsenal), 8 Katie Chapman (Chelsea), 11 Demi Stokes (Manchester City); 10 Jill Scott (Manchester City), 9 Toni Duggan (Manchester City).
Substitutes: 16 Karen Carney (Chelsea) for Stokes 56, 18 Eniola Aluko (Chelsea) for Duggan 64, 17 Gemma Davison (Chelsea) for Chapman 78.
Substitutes not used: 12 Lucy Bronze (Manchester City), 13 Carly Telford (Notts County), 14 Laura Bassett (Notts County), 15 Gilly Flaherty (Chelsea).
Head coach: Mark Sampson
Goal: Jill Scott 84
Booking: Greenwood 71
Belgium: 1 Justien Odeurs, 3 Heleen Jaques, 4 Maud Coutereels, 5 Lorca Van de Putte, 6 Tine de Caigny, 9 Tessa Wullaert, 10 Aline Zeler (C), 11 Janice Cayman, 14 Lenie Onzia, 20 Julie Biesmans, 22 Laura Deloose.
Substitutes: 13 Sara Yuceil for de Caigny 90, 15 Tine Schrijvers for Wullaert 90+3
Substitutes not used: 2 Davina Philtjens, 8 Cecile de Gernier, 12 Nicky Evrard, 17 Jana Coryn, 23 Elien van Wynendaele.
Head coach: Ives Serneels
Goal: Cayman 18
Referee: Gyongyi Gaal (HUN)
Source / photo – www.thefa.com