ITV's Ian Griffiths moved to a newly created combined role of chief operating officer alongside his previous position as group finance director following confirmation Crozier was leaving ITV in May.
McCall, who takes over from previous incumbent Adam Crozier, who left in June, seven years after taking over the reins at ITV, is stepping down as CEO of low-priced airline easyJet to take up her new role.
McCall joined EasyJet in 2010, turning the company into one of Europe's key airline carriers, and before that was CEO of Guardian Media Group.
For the past seven years McCall (below) has been running easyJet - where she's done pretty well although easyJet is now suffering badly from the sinking pound (which sends up its fuel costs) and a slowdown in United Kingdom consumer spending - but she's best known in media land for her spell as CEO of Guardian Media Group, which looked as though it was on the brink of finally escaping endless losses. It is a fantastic company in a dynamic and stimulating sector.
"I'm delighted we'll be working together at ITV".
However, since joining EasyJet in July 2010 McCall had overseen a steady rise in share price rise of more than 200pc, or 914p, to 1347p.
Crozier oversaw the company for more than seven years and led its transformation from an advertising-dependent networks company into a broader business with a big production arm, which he expanded via acquisitions, and digital assets.
During her tenure at EasyJet, McCall brought a customer-focussed approach to the business and redefined what passengers now expect from short haul flights.
Dutchman at centre of new European horse meat scandal
The animals were slaughtered and processed, then sent on to Belgium, which is among the largest horsemeat exporters in the EU. Mislabelled meat products were later found on supermarket shelves in a number of European countries, including the UK.
ITV described it as "broadly the same remuneration opportunity" to Mr Crozier's.
She worked her way up in the media company after starting as a research planner and became a close ally of former Guardian editor Alan Rusbridger.
easyJet will now begin the search for a new chief executive.
ITV will pay McCall an annual salary of £900,000 and a pension allowance of 15 percent of her pay.
In May, ITV said it expected an 8-9% fall in ad revenue in the first half.
McCall was said to have been chosen as the preferred candidate for the ITV top job at the end of last month, but reports have said that disagreements about her salary package had slowed things down.
McCall has been chief exec at budget airline EasyJet for the last seven years.