Butland, who pulled off a string of fine stops throughout normal and extra time, saved from Eden Hazard after all the previous nine spot-kicks had been converted to decide a tense contest that Chelsea had dragged themselves back into at the death in normal time.
Jonathan Walters struck a goal worthy of winning any contest to give Stoke the lead early in the second half before Loic Remy’s injury-time equaliser took the tie the distance at the Britannia Stadium.
Despite seeing his team outplay Stoke for much of the game on Tuesday, Mourinho was subjected to 'sacked in the morning' taunts from the home side's supporters as Chelsea suffered another significant setback following a poor start to their Premier League title defence. An injury blow to Diego Costa compounded matters further.
For Stoke, who had Phil Bardsley sent off, the victory was a welcome return to the form that saw Mark Hughes' men win four games in a row before defeat against Watford on Saturday, and few sides will want to face them in the League Cup quarter-finals.
Chelsea began brightly and Costa's cross-cum-shot was cleared off the line by Glenn Whelan, while former Stoke goalkeeper Asmir Begovic had barely had a touch in the Chelsea goal when Marko Arnautovic fired a looping overhead kick just over the crossbar after 25 minutes.
Costa, who had picked up a knock, was removed after half an hour, while Hazard and Ramires felt the force of some heavy Stoke tackling as the hosts tried to unsettle Chelsea.
But the visitors continued to pile forward and Butland made a top-corner save from Hazard to keep the scores level, before John Terry's close-range finish was ruled out for offside.
Despite Chelsea's dominance, the best chance of the first half fell to Walters, but he failed to beat Begovic from point-blank range.
Walters more than made amends for his miss seven minutes after the break as he broke the deadlock in style. Charlie Adam's pass found him on the edge of the penalty area and Walters flicked the ball up before hitting a scorching half-volley into the top of the net, giving Begovic no chance.
The goal ignited the atmosphere inside the stadium, as the home crowd sensed they put Mourinho on the brink, and Walters went within inches of adding a spectacular second when he fired a scorching shot just over from 20 yards.
Just as it seemed Stoke's battling performance had drained the fight out of Chelsea, Kurt Zouma flicked a corner on to Remy, who lashed the ball into the top of the net from close range.
Stoke were then reduced to 10 men when Bardsley was shown a second yellow card for a cynical challenge on Kenedy.
Chelsea
were buoyant in extra-time and Hazard came close to winning it when he
hooked a shot just wide with Butland at full stretch.
Butland's
outstanding performance in the first 90 minutes continued
throughout extra-time and it was his save from Kenedy in the dying
moments that took the tie to penalties.
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