Deloitte will take over the firm's 238 stores after attempts to save the troubled music retailer, which has over 4,000 employees, failed.
HMV has suspended its shares on the London Stock Exchange but its shops will remain open while Deloitte assesses the business and seeks potential buyers.
The company's board of directors met earlier this evening (January 14) to discuss their options, following failed requests to the firm's suppliers for £300 million in additional financing. It was hoped a third party would come to the rescue.
A HMV statement said: "The board regrets to announce that it has been unable to reach a position where it feels able to continue to trade outside of insolvency protection.
"It is proposed that Nick Edwards, Neville Kahn and Rob Harding, partners of Deloitte LLP, will be appointed as the administrators of the company and certain of its subsidiaries.
"The directors of the company understand that it is the intention of the administrators, once appointed, to continue to trade whilst they seek a purchaser for the business."
The 91-year-old chain faced difficult trading conditions at Christmas, owing £176 million to banks and experiencing a sales slump due to competition from online retailers.
The news comes just days after photography retailer Jessops was forced to close all of its 187 UK stores.
HMV is currently run by Trevor Moore, who only recently took over as chief executive after leaving Jessops.