The laid-back right-hander has a National League Cy Young to his credit, as well as an All-Star Game performance and a 42-inning scoreless streak earlier this year.
But until Wednesday night, he'd never pitched in the postseason, which begged the question of how he would handle being on the big stage for the first time.
The answer, it turned out, was just fine. Well, actually better than fine.
Webb set the tone for the D-backs as he outdueled Cubs ace Carlos Zambrano to help Arizona pick up a 3-1 victory in Game 1 of the NL Division Series.
"It was a big day for him, and it was huge for us to get that first one," center fielder Chris Young said.
Indeed, with the D-backs' next two scheduled starters, Doug Davis and Livan Hernandez, both having their share of struggles lately, Arizona could ill afford a stumble by its ace, especially at home.
Webb did anything but as he allowed just one run on four hits over seven innings.
"He never ceases to amaze me," outfielder Eric Byrnes said. "The guy is not fazed by it. He's a Cy Young Award winner. He's not going to let something like the postseason get in the way of what he does."
Webb went through his normal pregame routine, which is to say he did whatever he felt like during the day. While he used to eat before every start at the local IHOP, Webb nowadays eats anywhere. Wednesday, his pregame meal was a sandwich from a local Chick-fil-A restaurant.
"I thought I'd be a little bit more nervous," Webb said. "And I was a little bit the first few pitches, but I was able to calm those pretty quick. I didn't feel it was a must-win game. Obviously, we want to go out there and win every ballgame. It was a huge win for us, but I don't think it's a must-win when we've still got a bunch of games left."
It certainly helped Webb's nerves that he had his good sinker going right from start. His curve and change have also been big for him this year, but everything works off the sinker.
"That was one of his better games," catcher Chris Snyder said. "That was the Webby you saw during the 42-inning streak."
It was Zambrano who gave Webb his first taste of trouble when he doubled to lead off the third inning, but he was stranded there as Webb managed to strikeout Alfonso Soriano, Jacque Jones and Derrek Lee in order. Soriano swung through a curveball, while Jones did likewise on a changeup and then Lee was caught looking at a fastball.
"Lot of sinkers and threw some good changeups to put guys away and threw some good curveballs for strikes just to keep them honest," Snyder said.
Stephen Drew gave Webb a lead to work with when he led off the fourth with a 432-foot home run to right-center off a 92-mph fastball from Zambrano.
The Cubs were able to push across a run in the sixth when Webb temporarily lost his feel for the strike zone.
Lee led off the inning with a single and Webb quickly got two outs before walking Mark DeRosa and Geovany Soto to load the bases.
"From the stretch I was rushing a little bit and dragging my arm," Webb said. "I was jerking those fastballs inside to lefties and away from righties. I was able to get back on top."
He did, but not before Ryan Theriot bounced a chopper that just got over the glove of a leaping Mark Reynolds at third, which allowed Lee to score. Drew was able to backhand the ball just before it got to the outfield which forced DeRosa to hold at third and Webb got Zambrano to strike out on a curve to end the inning with no further damage.
The game didn't stay tied for long as Reynolds, who began the year in Double-A Mobile, led off the seventh inning with a homer off reliever Carlos Marmol, who had come in for Zambrano.
One out later, Snyder drew a walk, moved to third on Augie Ojeda's double and then came home when Conor Jackson, pinch-hitting for Webb, lifted a sacrifice fly to center to give Arizona a 3-1 lead.
"I was just looking for something to get elevated, pretty much," said Jackson. "I figured with a base open I was going to see more offspeed than anything. I got an 0-1 curveball or slider. [Marmol] has got nasty stuff though."
From there, the D-backs turned things over to their bullpen, which has come through on so many occasions for them this year.
Setup man Brandon Lyon retired the Cubs in order in the eighth and Jose Valverde, who led the Majors in saves with 47 during the regular season, closed things out in the ninth.
"It's nothing new for us, this is how we roll," Jackson said. "We get an early lead and we keep it. If we get down, we come back and get one more run than they do and keep it. It's what we've been doing all year long. So this is a big win, but it's not a surprise that we held the Cubbies to one run. It's a solid offense, but tonight our starting pitcher and our bullpen were phenomenal."
Steve Gilbert is a reporter for MLB.com. This story was not subject to the approval of Major League Baseball or its clubs.