Following an astonishing run of seven successive victories since the summer break, four-times champion Vettel is poised for number eight after clinching the 44th pole of his career.
Vettel snatched top spot in typically dramatic style as Webber was sitting pretty at the top of the timesheet, although made an error in the final part of the track.
It proved decisive because on his final run long after the clock had signalled the end of the 10 minutes for the final session, Vettel was down on Webber after the first two sectors.
The 26-year-old German, however, blitzed the last sector to take pole by 0.103secs to Webber for Red Bull's fifth front-row lock-out of the campaign.
It prompted a bizarre exchange of messages over the radio between Vettel and race engineer Guillaume Rocquelin in which they greeted the latest pole with the phrase 'shake 'n' bake' at one another.
That was a reference to the American comedy movie 'Talladega Nights: The Ballad of Ricky Bobby' about a NASCAR driver in which the phrase is used by Will Ferrell's character with regard to the blowing away of his opponents.
Asked as to the meaning in this case, Vettel said: "Well, he started it.
"There was a movie a couple of years ago about racing, which was more of a p***-take than an actual movie!
"It was a nice quote. It suits us being here in America, especially for my engineer who has a lot of history here given he did a lot of racing earlier in his career.
"So you need to ask him if it was what he used to say after securing pole position."
If Vettel blows away the field again come the race itself then the expression may well be used again, and will provide team principal Christian Horner with a welcome birthday present.
Horner celebrated his 40th on Saturday, and following qualifying was presented with a birthday cake by Vettel and Webber, only for the duo to end up coating him with it.
These are clearly party days for Red Bull in the wake of Vettel and the team landing their fourth consecutive titles recently.
For now, it is a private battle in races between Vettel and Webber as their rivals are nowhere, with Lotus' Romain Grosjean claiming third, but eight tenths of a second adrift of the 26-year-old German.
Vettel added: "It's a good result to have both cars on the front row, and a good battle with Mark.
"He has got closer and closer as the weekend has gone on. He might have had a mistake in his final shot, but I'm happy with pole.
"I like this circuit, and things are looking good as we did the job right. We're in the right place, and when that happens you want to win."
Webber openly held his hands up to his mistake as he said: "I had two shots (at pole) and the first part of my final lap was very good, but I didn't get turns 19 and 20 as I wanted.
"Sometimes you're happy but on this occasion I let pole slip through my fingers.
"It's not satisfying when you do that - it's not your job. But I'm happy to be there on the front."
Sauber's Nico Hulkenberg again qualified superbly, the German taking fourth ahead of Mercedes' Lewis Hamilton - a second behind Vettel - and Fernando Alonso in his Ferrari.
Jenson Button qualified 13th in his McLaren, but will serve a three-place grid penalty for overtaking under red flag conditions in first practice on Friday, so will start 16th, whilst Marussia's Max Chilton lines up 21st.
Pastor Maldonado, meanwhile, has suggested foul play by his team in the wake of a qualifying session which saw him grab 18th and team-mate Valterri Bottas ninth.
Notably, the duo were split by 1.5secs after the opening 20-minute run spearheaded by Bottas.