In a tweet published to his authenticated page on Wednesday, Mr Bezos said that he and his wife MacKenzie will divorce after 25 years of marriage.
According to the statement, the couple decided to divorce after a long period of "loving exploration and trial separation" and expect to continue as partners in joint ventures and projects.
"If we had known we would separate after 25 years together, we would do it all again," the tweeted message said.
The couple married in 1993 after they met at hedge fund DE Shaw in New York, where they both worked.
According to a 2013 profile in Vogue magazine, MacKenzie Bezos, 48, is an author who grew up in San
She attended Princeton University and met her husband when interviewing for a job at the hedge fund.
The couple were engaged after three months of dating and married three months after that, according to the magazine.
They have four children.
Speaking at an event in Berlin last April, Jeff Bezos acknowledged MacKenzie's support as instrumental when he founded Amazon in 1994, adding that she did the accounting for the company in its first year.
"When you have loving and supportive people in your life, like MacKenzie, my parents, my grandfather, my grandmother, you end up being able to take risks," he said at the time.
The announcement marked the second time Mr Bezos, 54, was in the news this week, after his company Amazon was named the world's most valuable company for a second time, replacing Microsoft.
Mr Bezos's fortune is believed to be as much as $137bn (£107bn), according to the latest real-time Forbes rankings.
Any financial details of the planned divorce and what impact the legal separation might have on the company are yet to be determined.