He will replace Benet Slay, who has been named as managing director for Diageo Northern Europe., a hub including France, Switzerland, Austria, Germany, the Nordics and Benelux.
Both appointments take effect from July 1.
Slay has been in his GB role since July 2006.
Litherland will move from his role as managing director for Brandhouse South Africa, a joint venture between Diageo, Heineken and Namibia Breweries.
Slay will retain his place as trustee of the Drinkaware Trust.