Atherton was offered the opportunity by the MCC in a sensitive gesture following his resignation as England's captain in the West Indies. The fact that Sachin Tendulkar, who gave up India's captaincy earlier this year, will be his opposite number adds a certain poignancy.
The 50-overs match, due to be played in front of a capacity attendance and televised live, will be one of the biggest MCC-organised occasions in Lord's history.
Roger Knight, secretary of the MCC, said the selections had been made with county commitments in mind - so no Brian Lara - and for one-day suitability.
He said: ``We're absolutely delighted with the response from the best players in the world. You never quite know when you first make the decision to put on the match.''
Steve Waugh, of Australia, declined an invitation because he had already committed himself to a Mother Teresa charity match in Calcutta.
An exhibition to mark the 150th anniversary of Grace's birth is to open in the Lord's museum on May 28.
The teams, MCC versus Rest of the World, will compete for the W G Grace Trophy, donated by Waterford and valued at £20,000. British Airways have agreed to fly in the players and their families free of charge.
In the event of rain, there will be no second day or Duckworth-Lewis computations to decide the winners.
James Whitaker, Leicestershire's captain, has been ruled out of their opening Benson and Hedges Cup game against Lancashire at Grace Road today because of a knee injury.
Whitaker is waiting for the results of a scan on the knee on which he had surgery during the winter. He aggravated the problem during last Sunday's AXA League win over Worcestershire.
All-rounder Vince Wells also misses the match because of flu so Aftab Habib and Dominic Williamson are included in a squad of 13.
MCC: M A Atherton (England), Aamir Sohail (Pakistan), M Azharuddin (India), S C Ganguly (India), B M McMillan (S Africa), -I A Healy (Australia), S K Warne (Australia) or A Kumble (India), J Srinath (India), A A Donald (S Africa), G D McGrath (Australia).
REST OF THE WORLD: Saeed Anwar (Pakistan), S T Jayasuriya (Sri Lanka), *S R Tendulkar (India), P A de Silva (Sri Lanka), G A Hick (England), T M Moody (Australia), -A Flower (Zimbabwe), C L Cairns (New Zealand), Wasim Akram (Pakistan), Mushtaq Ahmed (Pakistan), I R Bishop (West Indies).