However, two years on from her high-profile split from Brad, a love light for Jen reignited, with the Hollywood veteran striking up a romance with her Wanderlust co-star, Justin Theroux.
"I thought he was very sweet and he was always very nice," Jen once said of the lasting impression Justin, 46, had left on her heart during those first days of getting to know each other properly on set.
Sadly, today, it's another story for this pair; yes, the once-happily married couple have announced that they've ended their two-year marriage in December.
Here, we rewind the clock on Jen and Justin's relationship, reflecting on the love, hope and happiness that once burnt so bright…
A chance encounter, 2007
Jen first met Justin like we imagine most made-in-Tinseltown stars do: on the set of a Hollywood blockbuster. The movie? Tropic Thunder. Justin co-wrote the film with one of Jen's close friends, Ben Stiller.
Picking up where they left off, 2010
Jen and Justin's paths wouldn't cross again until three years later with the famed twosome coming together to co-star in the film Wanderlust. It is reported that Jen and Justin formed a friendship on set, before it trickled into a fully fledged romance.
Making things official, 2011
You're not a Hollywood 'It' couple until you make it official on an awards' show red carpet! Jen and Justin made their love publicly known at the MTV Movie Awards' afterparty in June 2011. And they didn't stop there with Jen taking Justin as her date to her acceptance of her Hollywood Walk of Fame star later that same year.
WATCH this video to see details of Jen and Justin's lavish LA wedding. Story continues after this video...
Cementing their Rome-ance, 2012
There's nothing quite as romantic as a marriage proposal, err, on your own birthday – right, Justin? Justin is said to have bent down on one knee and proposed to his love, Jen, at his 41st birthday at Greenwich Village's eatery Blue Hill in the Big Apple on August 10. The elated pair then celebrated the happy occasion with an Italian vacaction. When in Rome, no?
Feeling the love, 2014
From shutting down break-up rumours to laughing and cuddling on almost every red carpet of 2014, Jen couldn't help but gush about her then-fiance: "He's just so beautiful and handsome to me, and I love that his eyeballs are so beautifully captured because those eyes just knock me out every day," she said, according to Women's Wear Daily. "He just gets better every year."
Saying ‘I Do’, 2015
Not only was this a HUGE year for Jen, with the actress being nominated for a handful of awards for her role in Cake, but it is also the year she and Justin tied the knot at their lush Bel-Air mansion three years to the day that Justin first proposed.
Parting ways, 2018
The saddest of days have come: Jen and Justin announce they are parting ways after two years of marriage.
The couple confirmed the news of their split to the Associated Press, sharing it was "mutual and lovingly made at the end of last year".