Boots' deal covers this year's World Cup in France and runs until the 2021 European Championship in England.
"We are delighted to be partnering with Boots as the official partner of the England women’s team in what is a hugely exciting time for women's football,” said Mark Bullingham, FA chief executive and current chief commercial and football development officer.
"It's important we partner with brands that share our passion for raising the profile of the sport and the ability to help us do so."
It is the first time such a deal has included all five nations.
Women's soccer is gaining popularity and attracting growing financial interest, with Barclays bank last month becoming the Women's Super League's first title sponsor in another three-year deal reportedly worth over 10 million euros.
England are among the favourites to win the Women's World Cup after rising to third in the global rankings last month.
(Reporting by Karolos Grohmann; Editing by Ken Ferris)