Okay, this one immediately makes me think of 'The Hating Game' by Sally Thorne, but hear me out before you groan about how obvious that is. It's obvious for a reason. The whole plot is built on this foundation of professional rivalry that's so sharp you could cut yourself on it, and the ambition is just as much a turn-on for the characters as the attraction is. They're both clawing their way up, and watching them try to outmaneuver each other while secretly being obsessed is the whole point. The rivalry feels earned because their goals are genuinely in conflict; it's not just petty bickering.
Another layer I love is in 'The Unhoneymooners' by Christina Lauren. The rivalry starts as this deeply personal, almost familial competition—who's luckier, who's more successful—and then gets forced into the pressure cooker of a fake honeymoon. The ambition angle is quieter but still there, tied to job security and proving themselves. It morphs from petty one-upmanship into this reluctant alliance, which is a really satisfying arc.
For something with way higher stakes and a darker edge, 'The Kiss Quotient' by Helen Hoang flips the script. The ambition and rivalry aren't between the couple initially, but Michael's drive to provide for his family and Stella's competitive, analytical need to master relationships creates this fascinating power dynamic. They're rivals against their own circumstances more than each other, which builds a different kind of tension. The ambition to succeed, to not fail, becomes the glue that holds their unconventional deal together before it turns into something real.