Credit: EW

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When Matthew McConaughey met Camila Alves at an L.A. club in 2006, he was not looking for love.

“I was very happily single and healthily single,” the Free State of Jones star tells PEOPLE in this week’s cover story.

“I was not looking. I was sleeping well, I was spiritually sound, I was good hanging with me.”

And then he spotted Alves.

Kicking back with friends, including buddy Lance Armstrong, and making margaritas at their table, McConaughey, 46, says he all but stopped dead in his tracks. “Out of the corner of my eye, this sort of aqua-green figure went floating across the frame about 20 feet in front of me,” he recalls during an interview with PEOPLE and Entertainment Weekly‘s editorial director for an exclusive video series, The Jess Cagle Interview.

“My eye went up and I remember what came out of my mouth. I didn’t say ‘Who is that?’ I went, ‘What is that?’ As l was trying to get that’s attention across the room, I went in my head, ‘This is not the kind of woman you call over across the room, McConaughey. Get your ass out of your chair and go get her.’ Which I did.”

Nearly a decade — and three kids — later, it’s still easy for McConaughey to describe what immediately drew him to the Brazilian-raised Alves, 34. “The self-respect she had, the way I understood her and her relationship with family, the way she respected me but never took anything for granted, not putting on any airs whatsoever,” he says.

“We went on our first date three nights later and I knew then … I’ve been wanting to go on a date with her for the last nine years and not with anybody else.”

Watch McConaughey’s full Jess Cagle Interview above.