Baroness Campbell, 56, is the former boss of UK Sport.
During her time at UK Sport from 2003-2013, she oversaw a rise in the number of British medals won at the Olympics.
Kelly Simmons, the FA's director of participation and development, called Baroness Campbell "one of the most influential people in British sport".
"I'm really excited about helping shape the future vision and strategy for girls and women's football," said Baroness Campbell.
"Great strides have already been made both in terms of grassroots participation and at the elite level and I'm really looking forward to building on the work already done."
She will focus her work on increasing grassroots participation and getting further success for England's elite women's teams.
England reached the semi-finals of the 2015 World Cup, eventually finishing third with a 1-0 win over Germany.
Campbell, who will start her new role in March, is also chair of the Youth Sport Trust and was awarded a CBE for her services to sport in 2003.

According to parent company Liberty Global, Virgin Media originally said it had connected 465,000 new premises in the UK and Ireland in 2016.
But following a review, that number has been revised down to 314,000.
Liberty said Virgin had exaggerated how fast it could complete the connections.
In a regulatory filing, the US company explained that - under Virgin's own reporting standards - the figures included premises where installation work was "essentially complete" but not actually finished.
That included 142,000 sites that had been expected to be connected during the first three months of 2017.
However, Liberty said that in late February 2017, it had discovered that "the construction work necessary to connect a substantial number of [these premises] had not progressed as originally understood".
This prompted it to carry out a review, in which it found "the completion status" of some premises had been "misrepresented".
Liberty also said Virgin Media had "inadvertently" classified a further 9,000 unfinished premises as connected, when they had not been.
Dan Howdle, a consumer telecoms analyst at Cable.co.uk, told the BBC: "Clearly the way in which the numbers had been reported failed to preclude the possibility of jumping the gun, though there is no evidence an intent to mislead lay behind it."
He added: "Virgin Media appears to be dealing with the issue decisively, though mistakes resulting in stories of this nature are unlikely to leave a brand completely unscathed."
Four Virgin Media employees have been suspended in connection with Liberty's investigation and could face disciplinary action "including dismissal".
The company said the setback would affect the total number of premises Virgin Media connected during the first half of 2017.
However, it said it had taken steps to speed up Project Lightning, including appointing a new managing director, Robert Evans, to lead the scheme.
It also said Virgin would no longer include uncompleted connections in its figures.
Launched in 2015, Virgin's Project Lightning is designed to connect about four million more UK homes and businesses to broadband speeds of 300Mbs.
By the end of December it had reached 567,000 premises in total - down from the 718,000 previously reported.

The Harrogate Autumn Flower Show will use specialist technology to ensure the winning fruit is of the Gigantomo variety.
The giant entries must be from that strain of plant to win the Â£1,000 prize.
It comes after competitors raised concerns unscrupulous growers might sneak in a rogue type of tomato.
Show director Nick Smith said they wanted to be certain the winner "had the right pedigree."
"Giant veg growing is great fun and tremendously popular with our visitors, but it also has a serious side, especially with such a big prize at stake," he added.
The Gigantomo class, developed for its huge red fruits, was launched in January, with the final weigh-in on Friday.
Plant specialist and prize sponsors Van Meuwen said it is the product of almost two decades work by breeders in the UK and United States.
Dutch specialists will test the plants to make sure the entries are what they claim to be and the winner could scoop a further Â£5,000 if the heaviest fruit sets a new world record.
The Guinness record for the heaviest tomato stands at 7lb 12oz (3.5kg).
The Football Association says Baroness Sue Campbell's appointment as its new head of women's football is a "massive statement".
[NEXT_CONCEPT]
Virgin Media has suspended four members of staff and begun an investigation after it admitted overstating the expansion of its superfast broadband network, dubbed Project Lightning.
[NEXT_CONCEPT]
Gardeners trying to cheat their way to the top tomato prize at a horticultural show will be weeded out with DNA tests.