Ms McCall will begin the role in January 2018 as she succeeds Adam Crozier, who stepped down from the broadcaster at the end of June.
The 55-year-old, who was chief executive of Guardian Media Group before joining Luton-based easyJet in 2010, said she was "really pleased" to be joining ITV.
"It is a fantastic company in a dynamic and stimulating sector," Ms McCall said. "I am looking forward to getting to know all of the people at ITV and helping it make the most of the amazing opportunities that it has in the future."
ITV chairman Peter Bazalgette hailed Ms McCall’s appointment.
"In a very impressive field of high calibre candidates, Carolyn stood out for her track record in media, experience of an international operation, clear strategic acumen and strong record of delivering value to shareholders," he said.
Ms McCall will receive an annual salary of £900,000 and a pension allowance of 15% of salary. She will also be eligible for a bonus plan up to a maximum of 180% of salary and a long-term incentive plan up to 265% of salary.
Alongside her role at the low-cost airline, Ms McCall has been a non-executive director of Burberry since 2014.
She also sits on the board of the Department of Business, Energy and Industrial Strategy and is a Trustee at the Royal Academy.