Greg Greeley, who was vice-president of Amazon Prime, joins Airbnb this month as president of homes.
Greeley will oversee the day-to-day operations and strategy of the main home-renting business.
Greeley had been at Amazon since the very early days and was instrumental in expanding Amazon's Prime membership program to new markets.
He also ran Amazon's European division and most recently worked on the integration of the Whole Foods business which was acquired by Amazon in a multi-billion dollar deal.
"I've used Airbnb for years and the chance to work here and expand the positive impact its community is having around the world is a once in a lifetime opportunity," Greeley said.
"It has been an amazing and inspirational experience, but the time has come for me to take on a different challenge."
The Homes division is Airbnb's main business which also includes separate entities Trips, Luxury and its standalone China business.