The shock departure ends a two-year stint at the OTA during which time he has overseen growth in markets around Europe, with particular successes in France.
However the growing involvement of technology provider Amadeus, which increased its stake to around 75% last year, ended the initial ownership structure of support from nine leading European airlines.
Vincent said: “I have thoroughly enjoyed my time at Opodo and the decision to leave has been an extremely hard one to take.
“However, I have been offered a significant career opportunity by one of the world’s leading hotel brands that was simply too good to turn down.
“I would like to thank the Opodo Board and the Opodo team for their support over the past 2 years.”
Vincent is expected to take up his new post in the New Year, but will oversee the appointment of a replacement at Opodo.
Philippe Chérèque, senior vice president for corporate strategy at Amadeus. said: “We are sorry to see Simon leave and we would like to thank him for his significant contribution to developing the Opodo business across Europe in the last two years.
“At the same time we wish him well in his new career at Hilton.”