The role will see Hughes head up the 15-strong online content and display team within HMV, reporting to HMV marketing director Graham Sim.
Hughes was with Amazon for five years in its media department. Prior to this she held roles with media wholesaler Entertainment UK and high street retailer MVC.
HMV recently announced its online sales in the 52 weeks to April 25, 2009 were up 16%.
In September it acquired a 50% stake in the London-based MP3 store 7digital.com for £7.7m, making it the exclusive supplier of HMV's digital content.