The US-owned internet giant declined to comment on the reasons for Paine's departure, but it comes at a time when a string of media companies are on the lookout to hire online talent to meet the huge increase in internet traffic and advertising volumes.
Paine, who before joining AOL worked as a media director for McCann-Erickson in Russia, had responsibility for sales strategy, planning, research and trade marketing, working under Andy Jonesco, vice president of Interactive Marketing for AOL UK.
His departure comes with AOL UK planning to unveil a revamp of its free-to-view AOL.co.uk website, as part of a shift towards offering free content funded by advertising, as opposed to its long running subscription-based strategy.
As well as heading AOL's strategy, Paine has also been a key mover within the Internet Advertising Bureau.
It is not known if he is to resurface at one of AOL's rivals, although the likes of MSN, which is looking to double its sales team, and Yahoo!, which has recently hired a string of sales people, are known to be aggressively ramping up their advertising operations.
There is currently a major recruitment drive across the internet sector, both from the media owner and agency aside.
Paine's departure from AOL is the latest in a series of moves within its marketing operation, including the resignation of vice president of marketing Sharon Lang in January and the arrival of former Orange marketing manager Timothy Ryan to the new role of brand director.
It also comes with AOL part way through a review of its European media planning and buying account, held by Vizeum in the UK, where it is worth £35m in billings
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