AOL People Networks president Joanna Shields, who joined the company after AOL's $850m acquisition of Bebo last year is to step down from her role to pursue entrepreneurial interest in London.
Shields is the third key figure to exit AOL since ex-Google sales chief Tim Armstrong took over AOL in March, following the departure of former CEO Randy Falco and Platfrom-A president Greg Coleman.
Armstrong said Shields will continue to act as an adviser to AOL.
In a memo to staff, Shields said: "It has been a remarkable year and I feel incredibly lucky to have spent this time with you.
"I have been blessed to be part of many success stories in the past from RealNetworks and Google through to Bebo and my time with you at AOL will go down as one of my proudest."
AOL's People Networks, which includes its AIM and ICQ instant messaging services introduced a number of initiatives under Shields, including the acquisition of its social networking aggregator Socialthing and Bebo's Social Inbox.
No replacement was named to run People Networks, however, AOL said the division would not be shutting down, and in fact, is planning on launching new instant messaging products in a number of months.
Shields' departure comes at a time when AOL begins to restructure itself in preparation for a spin-off from parent company Time Warner.
Armstrong is expected to lead the new company and has been pruning management to form a more centralised structure.
A final decision about AOL's future is expected to be made tomorrow during a meeting of the board of directors.
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