The 34-year-old wicket-keeper batsman, who played the last of his 69 Tests for Pakistan last year, will lead a squad of seven players which includes only two newcomers to international cricket.
Hong Kong Sixes Tournament 2005 is being played at Kowloon Cricket Club October 22-23 with teams from seven Test nations and hosts Hong Kong featuring.
The other members of the Pakistan team are Yasir Arafat, Naveed Latif, Mohammad Hafeez, Tahir Khan, Kamran Hussain and Riaz Afridi.
"It's a great honour for me because I have represented Pakistan in the Super Sixes before and have won the title," said Khan, who still harbours hope of an international comeback.
Khan praised cricket interest and facilities in Hong Kong.
"They stage two events in Hong Kong every year, the main Super Sixes and the Plate event which attract good crowds," said Khan.
The Hong Kong Sixes has been a popular attraction for all the major cricket playing countries since its debut in 1992.
Each team plays with six players, all of whom have to bowl and bat. A batsman is retired after scoring 30 runs.
Pakistan won the inaugural event in 1992 with former left arm pace bowler Wasim Akram as captain, and captured the title again in 1997, 2001 and 2002.
Pakistan will line up in Pool B for the preliminary round of the matches, alongside India, South Africa and West Indies while England line up in Pool A with arch rivals Australia, Sri Lanka and hosts Hong Kong.
England, who have appointed former off-spinner Robert Croft as their captain, bid to win three titles in a row after winning the event in 2003 and 2004.
The Hong Kong Super Sixes 2005 will have a record prize money of 280,000 dollars with the winners receiving 100,000 dollars.