Maroon 5 guitarist James Valentine reminisces on band's first hit "Harder to Breathe" in new TV documentary

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Maroon 5 have landed 24 songs on the Billboard Hot 100 chart in the past 14 years, but it all started with one hit.

In 2002, the Adam Levine-fronted act released their breakout single, “Harder to Breathe.” The debut went on to peak at No. 18 and launch the band to become one of the biggest chart-topping groups in mainstream pop music today.

On Sept. 16, the music documentary series Ernie Ball: The Pursuit of Tone will highlight Maroon 5 guitarist James Valentine, and he’ll discuss the band’s Grammy-winning success, bandmate Levine’s role on NBC smash The Voice and more.

“I was very happy that they decided to feature me on the show. I’ve been a fan of this series for a while; they do an amazing job,” Valentine, 37, tells PEOPLE exclusively. “As a guitar player, I love watching the series to see other players’ approaches, but I think people will enjoy hearing the stories even if they’re not interested in guitar. I think it will give people a unique insight into the inner workings of Maroon 5.”

PEOPLE has an exclusive first look at the episode, and he dishes on their breakout hit – and pal Levine’s own string skills.

“‘Harder to Breathe,’ it’s one of the heavier songs on Songs About Jane,” Valentine says in the clip of the hit off their debut LP. “It’s more of a straight-ahead rock song, and it was kind of a funny reason, but the guys who worked at our record label, they were kind of figuring out the best way to get us on the radio, and they had some relationships with modern rock radio, so they wanted to lead with a more aggressive rock-sounding sort of song, so they picked “Harder to Breathe.”

And while Maroon 5 has performed the track countless times, between at awards shows and on international tours, Valentine thinks it’s an oldie but a goodie.

“It’s still so much fun to play because I get to crank up,” he says in the clip.

As for Levine, Valentine said the frontman is much more than a killer vocalist.

“Most people don’t know this, but Adam is a great guitar player: On ‘Harder to Breathe,’ we both played solos,” he says in the clip.

On Sept. 3, Maroon 5 kicked off the second leg of U.S. stops on their latest tour: When it ends next year, the band will have played more than 120 shows in more than 30 countries for more than 2.5 million fans.

Valetine’s episode of Ernie Ball: The Pursuit of Tone airs Sept. 16 on the Audience Network.