The 51-year-old former Netherlands international saw his side lose 2-0 to the Czech Republic on Sunday after a perfect group stage.
The Dutch Football Association (KNVB) confirmed they had parted ways with de Boer who released a statement.
“In anticipation of the evaluation, I have decided not to continue as national coach. The objective has not been achieved, that is clear,” de Boer said.
“When I was approached to become national coach in 2020, I thought it was an honour and a challenge, but I was also aware of the pressure that would come upon me from the moment I was appointed, that pressure is only increasing now, and that is not a healthy situation for me, nor for the squad in the run-up to such an important match for the Dutch football on its way to World Cup qualification.
“I want to thank everyone, of course the fans and the players. My compliments also to the management who have created a real top sports climate here on campus.”
De Boer had been in charge of the Dutch since 2020, signing a deal until the end of 2022.
He took over following a tumultuous period for the national team, having missed out on qualifying for both the 2016 Euros and the 2018 World Cup with numerous changes in manager, including Guus Hiddink, Dick Advocaat, Danny Blind and Ronald Koeman.
KNVB Director of Football Nico-Jan Hoogma said: “Despite Frank’s efforts, the goal of reaching the quarter-finals was not reached. Our choice for Frank turned out differently than we hoped.
“Now I need to find a successor. Let it be clear that we are not satisfied. We would have probably made this same decision on our own in the next two days.”