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They'd begun casually dating after working together on Lowe's 1990 erotic thriller, Bad Influence, and he saw something truly special in Sheryl, then a renowned makeup artist (now a fine jewelry designer).
"I had the feeling that if I was ever going to be able to make it work with anybody, it was Sheryl," Lowe tells PEOPLE in this week's cover story, recalling feeling "seen" for the first time in his life.
A big issue, however, was that Lowe, 57, wasn't yet sober or particularly good with commitment. "Intimacy and I were not very well acquainted, until very late in my life," he says.
But Lowe was already nearing a crossroads, and it became increasingly clear his fast-lane lifestyle and a future with Sheryl, 60, were incompatible.
"Alcohol and drugs were only going to make that next to impossible," he recalls.
getty Rob Lowe and wife Sheryl
Lowe eventually went to rehab and embraced what would be a lifelong commitment to his recovery — and to Sheryl.
Sober and grateful for his new path, the two married in 1991 and welcomed sons Matthew in 1993 and John Owen two years later.
"I'm happy I lived the life that I lived because I have no regrets, but I was super ready to coach Little League, carve pumpkins on Halloween, read books and serve hot lunch on Wednesdays," says Lowe, who will celebrate 32 years of sobriety in May. "I really, really loved every minute of it."
getty Rob Lowe and wife Sheryl
For more from Rob Lowe and his 30-year marriage with Sheryl, pick up the latest issue of PEOPLE on newsstands Friday, or subscribe here.
Throughout his run on The West Wing from 1999 to 2003, he commuted the 82 miles between their home in Santa Barbara and L.A. daily, so he could be with the family and kiss the boys at bedtime.
"They knew I was there and I felt like that was of value," Lowe says.
Watch the full episode of People Cover Story: Rob Lowe on PeopleTV.com or on the PeopleTV app.
The actor remains forever grateful that Sheryl, owner of Sheryl Lowe Jewelry, took a chance on him. "She saw things in me that nobody had ever seen before," he says, calling his 30-year marriage to Sheryl one of life's greatest "miracles."
"I still think she's the hottest, sexiest, most beautiful, insane, complicated, entertaining person that I know, in addition to being a great mother," he adds of his wife.
Jonny Marlow Rob Lowe
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For their part, sons Matthew, 28, a lawyer, and John Owen, 26, a TV writer, feel fortunate to have grown up around such love — and aren't above taking advice from their dad.
"He's great with relationship advice," says Matthew. "He'll say, 'When I found your mother, I knew she was the one. I married my best friend, and it's worked out perfectly for me. So take that advice.' ... He gives little pearls of wisdom like that that I keep with me. Hopefully, I will end up in a 30-year marriage like him."