Charles, who joins on 6 March, will be asked to handle the launch of Virgin's Dubai route at the end of March, while a new service to Jamaica launches in July.
He pledged to help maintain the airline's reputation for 'best customer service and innovation', adding that he expected to work closely with Sir Richard Branson, who personally approved the appointment.
Charles will report to CEO Steve Ridgeway and sit on the airline's senior management group.
Through regular broadcast appearances he has established himself as the face of a confident brand since joining Eurostar three years ago. His successor will oversee the 2007 terminus switch from Waterloo to St Pancras.
Charles's move sees him turn his attention from battling short-haul airlines to Virgin's rival carriers.
He was PRWeek's PR Professional of the Year in 2004.