The 60-year-old has decided to cut short his spell with the Dutch national team after a tumultuous campaign at the Euros where they suffered three defeats from as many games
The 60-year-old's position had been under threat after Oranje crashed out of Euro 2012 at the group stage with three defeats from three matches.
He also faced strong criticism from players and media alike and reportedly lost control of the dressing room after rebellion led by vice-captain Rafael van der Vaart.
After a meeting between Van Marwijk and the KNVB, both parties decided that the coach's contract, which was due to expire in 2016, would be terminated with immediate effect.
"We are grateful to Van Marwijk," KNVB director Bert van Oostveen said. "He performed exceptionally well at the 2010 World Cup and in getting us to the top of the Fifa World Ranking.
"Of course it is sad to part company with him, but we must be realistic."
Van Marwijk took charge of Netherlands in 2008, replacing Marco van Basten, and guided Oranje to a runners-up finish at the World Cup in South Africa.
He also led the Dutch side to an impressive campaign in the Euro 2012 qualifiers, winning nine out of 10 matches, but in Poland and Ukraine they suffered defeats to Germany, Portugal and Denmark.