The deal, which covers major UK cities including Liverpool, Leeds, Glasgow and Manchester, means CBS now has all of the major bus fleets contracted for next year.
Arriva operates 1,500 buses in London, covering 19% of the capital's bus fleet, and runs fleets in Wales, the Home Counties and the Midlands.
CBS has also pledged to plough fresh investment into the Arriva inventory, which will include the introduction of illuminated formats and digital signage this year.
Jason Cotterrell, commercial director of CBS Outdoor, said the contract win was "a great endorsement of our proposition and ability to capture and captivate consumers on the move".
CBS has held the Arriva contract since 1995 and faced competition for the contract from Titan.
Mark Yexley, managing director of Arriva London, admitted CBS overcame "strong competition" for the contract.
But he added: "We were influenced by their strong track record in driving the industry forward and delivering increased revenues for Arriva."
The Arriva inventory is likely to become increasingly important. Research by the Passenger Transport Executive forecasts that bus journeys in London will increase by 4.4% by 2011.
Meanwhile, Transport for London believes public transport capacity will need to grow by 40%.