High street chemist Boots will sponsor the home nations and Republic of Ireland women’s teams for three years.
It is the first time such a deal has included all five nations.
Last month, Barclays bank became the Women’s Super League’s first title sponsor in a three-year deal understood to be worth in excess of £10m.
UK car maker Vauxhall ended its deal – thought to be worth £5m to £6m a year – with the men’s home nations teams after the 2018 World Cup.
Boots’ sponsorship includes this summer’s World Cup in France and the 2021 European Championship in England.
England women, ranked third in the world, and Scotland, ranked 20th, will face each other in Group D of the World Cup, which begins on 7 June.
Wales are 33rd in the world, with Northern Ireland 59th and the Republic 31st.
Mark Bullingham, chief commercial and development officer at the Football Association, said England were “delighted” to partner with Boots.
“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,” said Bullingham, who will replace Martin Glenn as FA chief executive at the end of the season.
“I look forward to seeing us work together to make the Lionesses household names and inspiring the next generation of girls to take up the game.”
The deal follows England boss Phil Neville calling on Manchester United, Chelsea and Arsenal to “throw open” their stadiums for women’s football matches.
There have been high attendances recently for women’s matches across Europe, including a top-flight domestic record of 60,739 as Barcelona beat Atletico Madrid on 17 March.
Boots will not be the title sponsor for Northern Ireland, with the Irish FA stating the deal covers health and wellbeing initiatives only.
Northern Ireland manager Alfie Wylie said: “We welcome this support from Boots as the health and wellbeing of players is paramount across the many women’s and girls’ football programmes throughout Northern Ireland.
“We look forward to developing this relationship with Boots over the coming years.”