Hunt is currently the BBC's controller of daytime and early peak television, and will take up her new post overseeing programming for Five's core channel later this year.
Hit shows she will oversee for the channel include 'House', 'CSI: Crime Scene Investigation' and 'Grey's Anatomy'.
She joined the BBC as a researcher on 'BBC Breakfast News' in 1989, and went on to work for 'Newsnight' and 'Panorama' as an output editor and senior producer.
Hunt then became editor of the 'One O'Clock News', before moving to the editor's chair at the 'Six O'Clock News' in April 2001, where she later oversaw the programme's relaunch.
She moved into daytime television at the end of 2003, first as an executive producer in Birmingham, then as a senior commissioning executive, before becoming controller of daytime in May 2005, adding early peak to her responsibilities in March 2007.
Lisa Opie, Five's managing director of content, said: "I am thrilled we have been able to appoint an executive as creative, dynamic and energetic as Jay.
"Her record of success at the BBC speaks for itself and I'm excited that one of the most astute operators in the business is becoming part of the Five team."
Hunt said: "The prospect of building on Five's existing successful programming and taking the channel to the next phase of its development is irresistible."
The appointment of Hunt marks the latest raid that Five has made on the BBC. The channel recently won Australian soap 'Neighbours' from the BBC, which it had aired for 21 years. Five already has the rights to 'Home and Away', giving it an Aussie double header.
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