It is understood that current Five chief executive Jane Lighting and chairman Remy Sautter will leave the company shortly.
Airey made her name in television by launching Five, home of 'Grey's Anatomy', 'Neighbours' and 'Home and Away', as director of programmes in 1996, going on to serve as chief executive between 2000 and 2003. She moved on to BSkyB as managing director of Sky Networks, leaving to join ill-fated start-up Iostar in early 2007.
ITV has temporarily appointed Lee Bartlett, chief operating officer of ITV global content, to Airey's role of managing director of global content. Airey hired Bartlett in March from Fox Broadcasting in the US, where he was executive vice-president of business affairs.
Michael Grade, executive chairman of ITV, said: "We have assembled a strong team to lead our global content business and they will now report to Lee. I will spend more of my time in the content business to ensure that the momentum is maintained."
ITV had given Airey, who it hired only in May last year, a war chest of £200m to acquire content production companies and a target of doubling the revenues of the division to £1.2bn by 2012.
Recent reports have linked Five's owner RTL, which has hired Airey, with interest in buying the 17.9% stake in ITV owned by BSkyB. Sky has been ordered by the government to sell down the stake to 7.5% at most.
RTL refused to comment on the changes at Five but said it would issue a statement in the coming days.