Darcey Bussell, the ballet dancer, Colin Jackson, the 110-metres hurdles world record holder, Richard Curtis, the director of films including Four Weddings and A Funeral, and Lord Foster of Thames Bank, the architect, will hold master classes in China.
Former England manager Sir Bobby Robson and David Davies, the executive director of the Football Association, will host a football master class and Mr Blair is expected to pose for photographs with Chinese footballers. Among 40 leading business figures also on the flight were the CBI director general, Sir Digby Jones, Sir Martin Sorrell, the chief executive of advertising giant WPP, Jan du Plessis, the chairman of British American Tobacco, JCB magnate Sir Anthony Bamford and the Kingfisher chief executive, Gerry Murphy.
On the return leg of the journey, the BA Boeing 747 carrying the Blairs and ministers, including Alan Johnson, the Trade Secretary, and Lord Powell of Bayswater, a former foreign policy adviser to Margaret Thatcher and now president of the China-Britain Business Council, will stop off in India.
The Blairs will be taken by helicopter to one of the world's most exotic hotels, Wildflower Hall, on the site of the former home of Lord Kitchener of Khartoum, high in the mountains of Shimla, the hill station that served as summer capital during the days of the Raj.
The Prime Minister boarded the plane at Edinburgh after visiting the Queen in Balmoral.
His office defended Mr Blair's decision to leave Britain with his wife only four days after returning from a month-long holiday in Barbados. His official spokesman denied he was neglecting domestic issues such as crime and the threat of terrorism.
"He is not spending his first week back from his holidays on foreign travel. He was out and about last Friday and he has been fully briefed.
"If you are fulfilling your role as the EU presidency, it is important to have good relations with these two countries which are important players in the world. It is also in our national interest that we have good relations with these countries. It is in our national interest to recognise the changing dynamic in the world."
Downing Street tried to stop the trade mission becoming bogged down in the on-going textiles dispute with the EU which has caused millions of pounds worth of clothes made in China to be held up at EU ports.
Peter Mandelson, the EU trade commissioner at the centre of the row, is already in Beijing trying to resolve the dispute. The Prime Minister's spokesman, in a clear attempt to distance Mr Blair from the row, said: "I suspect in general terms they will have discussions but the detailed negotiations continue to be a matter for the commission."
Britain's instinct was for free trade but as the current holder of the EU presidency, the UK also had to reflect the overall view of the commission, he said.
COLIN JACKSON, 38
The former sprinter and hurdler is Britain's most bemedalled athlete. He is now a commentator and TV presenter
DARCEY BUSSELL, 36
Joined the Royal Ballet in 1988 and became a principal in 1989. She is known for her faultless performances
SIR MARTIN SORRELL, 61
The chief executive of WPP since he started the advertising company in 1986. WPP is valued at £7.5bn
LORD FOSTER, 70
The architect's projects have included the Millennium Bridge, the 'Gherkin' and the Millau Viaduct in France
JAN DU PLESSIS, 51
The chairman of British American Tobacco since July 2004. He is also non-executive chairman of RHM
SIR BOBBY ROBSON, 72
Former footballer and manager of the England team. Now retired after being sacked by Newcastle United
RICHARD CURTIS, 56
The comedy scriptwriter is best known for the television series Blackadder and the film Four Weddings and a Funeral
SIR ANTHONY BAMFORD, 59
Retired as managing director of the construction group JCB last year, but still chairs the Staffordshire firm