Thomson spent 11 years with the company and moved up to the role of European president from the UK chairman and chief executive job in April this year.
Her departure follows the sale of AOL's UK ISP business to Carphone Warehouse last month. AOL is now restructuring as a portal-only business in the UK, France, Germany and the Netherlands.
Joe Redling, AOL president and AOL International chief executive, said d'Asaro Biondo was "eminently qualified for the role".
"He will bring renewed vision, energy, innovation and commitment to growing our web services business in Europe," Redling said.
Thomson joined AOL in 1995 as UK marketing director in the year prior to its launch over here.
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