The 'Spider-Man' star and the 39-year-old jewellery designer have decided to call time on their relationship but will focus on making sure their two children - Ruby, nine, and Otis, seven - are their top priority.
In a joint statement made to People magazine, they said: "After much soul searching and consideration we have made the decision to separate as a couple.
"As devoted parents, our first priority remains raising our children together with enduring love, respect and friendship."
The couple tied the knot in 2007 - four years after they met - in a ceremony in Hawaii in front of their close family and friends.
The 41-year-old actor has remained tight-lipped about his personal life throughout his career but previously gave an insight into their family life.
Speaking about welcoming their first child, he said at the time: "It's a very dramatic change. My whole life is in transition now with friendships and where I'm gonna live, you know? Just your whole perspective. It's great. Ruby's so adorable. She's just a smiley, little beautiful thing."
When the pair were preparing to tie the knot, Jennifer was thrilled, dubbing it the "best time of her life".
She shared: "Let’s just say this is truly the best time of my life. I’m walking on air. I’m getting married, starting a family and have an amazing company."
Tobey also opened up about wanting "security and comfort" in his life following a rocky childhood.
He explained at the time: "Growing up the way I did, I had a very serious ambition to make some money, to have some security and comfort in my life."