The fixture will take place at Mumbai's Police Ground on Thursday, a day after England's three-Test tour of India is due to conclude at the city's Wankhede Stadium.
"I am delighted to have the opportunity to lead MCC in this historic game against Afghanistan," said former England captain Gatting.
"Cricket has developed rapidly in the country over the last few years. MCC is keen to assist this process - as it is in all emerging cricket-playing nations."
Cricket's popularity in Afghanistan has increased since many of the refugees who fled from the country in the early 1980s, after the invasion by the then Soviet Union, started to return from Pakistan - where they saw the game and started to play and follow it.
In the last 10 years, the membership of the Afghanistan Cricket Federation has grown more than twenty-fold - from 500 to 12,000 members.
MCC President Robin Marlar, explaining the background to a fixture which marks the end of the club's own tour of India, said: "This match is the culmination of many months of hard work.
"It all started several years ago when an MCC member, Mark Scrase-Dickens, raised the issue of Afghan cricket at a club AGM (Annual General Meeting). "Subsequently, at the Asian Cricket Council in London last (northern) summer, I was asked to help and we have been so pleased with the contributions made by the World Cricket Academy in Mumbai and, of course, the authorities in Afghanistan who have been swift to seize the opportunity.
"This is merely the beginning," Marlar, the former captain of English county Sussex insisted.
"Because of the intensity of interest in the game in Afghanistan, there is no reason why that country should not progress year upon year with Bangladesh - the newest of the Test-playing nations - as the example to follow."
It is now more than three decades since MCC gave up its role as the governing body of English cricket, although that has done nothing to shorten the queue for membership with an average waiting list time of 20 years before candidates can wear the club's distinctive orange and yellow striped tie.
MCC remain the owners of London's Lord's Cricket Ground and are still the worldwide ruling body responsible for cricket's rules or Laws.
Another aspect of the club's work is in helping the development of cricket all round the world, especially in countries which are new to the game.
For example, in 2002, MCC helped organise a match between an Afghan XI and an international peacekeepers' side in the capital city of Kabul.
And the countries where MCC teams are due to tour later this year include China, Botswana and Zambia.