Walters went to ground in a tussle for the ball with Jamie Carragher and blasted home the resulting spot-kick.
Ryan Shawcross blocked a Luis Suarez effort with the Uruguayan prominent in Liverpool's attempts to draw level.
After the break Jordan Henderson should have equalised when he broke clear, while Suarez missed an open goal at the very end after an Asmir Begovic error.
Craig Bellamy came on to make his first appearance for Liverpool in his second spell for the club but the Welshman was unable to change the course of the game although he went close with a header.
Bellamy was introduced at the same time as Andy Carroll, who never really threatened a Stoke defence that was superb throughout, with Shawcross outstanding.
While Shawcross marshalled the Stoke rearguard, Walters' goal and performance overshadowed team-mate Peter Crouch, who was making his debut for the Potters against his former club.
After a promising start to the game, particularly in winning a number of free-kicks, Crouch faded and when Kenwyne Jones came on in the second half the former Spurs striker ran over to the bench only to realise that he was not being withdrawn.
Liverpool held steady under an early cumulative bombardment of free-kicks and Rory Delap's throws until the 20th minute.
Then the visitors' defence buckled when Carragher and Walters challenged one another in the box and with the Stoke forward going to ground, referee Mark Clattenburg was quick to award the penalty.
Walters crashed his spot-kick down the middle of the goal with Liverpool goalkeeper Pepe Reina diving to the right.
Both before and after Walters' goal Suarez carried Liverpool's main threat, with his movement and trickery giving Stoke all sorts of problems.
The Uruguayan flashed a shot over the bar in the opening stages of the game and then almost got a connection on the ball following a Charlie Adam corner.
Just after Walters' penalty Suarez was only denied a goal after Shawcross threw himself at the ball after Begovic had been unable to hold Henderson's cross.
Suarez then wriggled free down the left and crossed for Martin Skrtel who was unable to hit the ball cleanly under pressure from Matthew Etherington.
Henderson should have equalised when he broke clear in the second half after Luis Enrique threatened a pass through to the former Sunderland midfielder.
That he did not was due to sterling work by Begovic, who saved Henderson's effort, then quickly got up to save the rebound and was just as sprightly in getting back to his line to beat away an Adam shot.
Shortly afterwards Henderson and Kuyt were withdrawn with Carroll and Bellamy coming on, while Wilson Palacios also came on to make his Stoke debut.
The second half was played almost entirely in the Stoke half, but the likes of Matthew Upson, Shawcross and Begovic held firm under enormous Liverpool pressure.
Shawcross did well to get the ball ahead of Suarez as Stewart Downing crossed for the Uruguayan, while another cross from the Liverpool winger reached Bellamy at the far post but he headed his effort wide.
Late on Suarez claimed a penalty, arguing that Upson had handled the ball, while the former Ajax man should have secured a point for the visitors only to skew his shot wide with the goal at his mercy.
Source: BBC Sport
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