Frank Lampard also got on the score-sheet to become Chelsea's second-highest all-time goal-scorer, as Rafael Benitez's side bounced back from their 2-0 loss to Swansea City in the first leg of their League Cup semi-final.
Chelsea made the breakthrough in first-half injury time at the Britannia Stadium when Walters inadvertently put Cesar Azpilicueta's cross past his own goalkeeper with a bullet header.
Improbably, Walters then diverted a Juan Mata into his own goal to make it 2-0 in the 63rd-minute and two minutes later Lampard blasted home his 194th-Chelsea goal from the penalty spot after Mata went down in the Stoke box.
Stoke had not been beaten at home all season but that record was shattered, with Eden Hazard adding a superb fourth in the 73rd minute with a sweetly struck left-foot shot from 25 yards.
Chelsea fans had even more reason to cheer when captain John Terry came on as a substitute following a two-month injury lay-off, while Walters blazed a last-minute penalty over the crossbar to compound his misfortune.
Chelsea's victory took them back into third place, after the previous incumbents of the final podium position, Tottenham Hotspur, were held to a 0-0 draw at Queens Park Rangers (QPR).
Spurs striker Jermain Defoe came close to opening the scoring in the first half with a 20-yard strike that crashed back off the post, with QPR goalkeeper Julio Cesar reacting brilliantly to save Emmanuel Adebayor's follow-up.
The hosts' best chances both fell to Shaun Wright-Phillips, but he could not find the target on either occasion.
Julio Cesar also thwarted Defoe in the second period, while Tottenham full-back Kyle Walker whipped a free-kick inches over the crossbar.
Toppling the table
"They defended very well; we wanted to play with a higher tempo, but they frustrate you," said Tottenham manager Andre Villas-Boas.
"Julio Cesar had a great game. It was a difficult game for us, but we got an away point, so we are satisfied."
Following the shock 1-0 win at Chelsea in their previous outing, QPR are now five points from safety with 16 games to play.
They remain at the bottom of the table, however, after Reading avoided slipping to the foot of the standings by storming back from two goals down to win 3-2 in extraordinary fashion at home to West Bromwich Albion.
A Romelu Lukaku brace had put the visitors in control, but Reading scored three times in the last eight minutes through Jimmy Kebe, Adam Le Fondre and Pavel Pogrebnyak to give their fight to avoid relegation a shot in the arm.
Aston Villa's miserable week continued as they lost 1-0 at home to Southampton to slip into the relegation zone.
Beaten 3-1 by fourth-tier Bradford City in the first leg of their League Cup semi-final on Tuesday, Paul Lambert's men went down to a 34th-minute Rickie Lambert penalty and have now gone five league games without a win.
Wigan Athletic climbed out of the relegation places at Villa's expense after Franco Di Santo cancelled out Georgios Karagounis' 25-yard opener to give the Latics a 1-1 draw at Fulham.
A glorious 30-yard drive by Sebastian Larsson set Sunderland on their way to a 3-0 success at home to West Ham United that lifted them further away from the bottom three, with Adam Johnson and James McClean also on target.
Everton squandered an opportunity to close to within a point of fourth-place Spurs by drawing 0-0 at home to Swansea, while Newcastle United's trip to Norwich City also ended goalless.
The top two are both in action on Sunday, with leaders Manchester United hosting Liverpool and second-place Manchester City visiting Arsenal. – Sapa-AFP.