Charlesworth will take on the day-to-day operational management of Freeview, which is jointly owned by the BBC, Crown Castle and BSkyB.
At BSkyB, she had been strategic operations manager with a nine-year background in marketing and product development at the satellite television firm.
Charlesworth, who has already been working with Freeview while at BSkyB, joins as the free-to-air digital platform continues to see take-up rocket.
Last week, Ofcom said that the number of households with Freeview has rocketed by around 19% to 3.5m in the first quarter of 2004.
The media regulator's latest digital report showed that Freeview was the fastest-growing service in the market, with a 14% market share compared with 6% last year.
The growth is attracting new channels, with Disney planning to launch its first wholly advertising-funded UK television channel on the service.
At Freeview, Charlesworth will work to deepen and extend its relationships with manufacturers and retailers.
Andy Duncan, chairman of Freeview, said: "Freeview has been a great success story, and Lib's role is to build on this. Freeview has certainly proved to be a compelling proposition for the UK public, and I'm sure that this growth will continue."
Her appointment follows the departure earlier this year of Freeview's former general manager Seaman who joined Top Up TV, the new pay-television service.
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