The process will see Oddbins go to its creditors to tell them it cannot pay them in full, but ask if they will accept part restitution.
A CVA allows financially-troubled companies to reach agreement to pay creditors over an extended period of time.
Managing director Simon Baile blamed "legacy issues" around the acquisition of the chain from Castel - currently the subject of a high court dispute - and poor Christmas trading for the move.
But he insisted the business could be profitable and urged creditors to support it.
Baile told OLN: "It's a bloody good business - let's make it work."
He added: "We have been encouraged by the support that we have received from our supplier partners in recent weeks, who wish to continue to work with us to bring their products to a receptive market."
The news came after Oddbins' directors called in consultants Spectrum Corporate Finance and Deloitte to look at its financial situation.
Last week, Oddbins announced that 39 of its less profitable shops would shut.
The company said in a statement: "The core Oddbins business is profitable. We have proven through 2009 and 2010 that Oddbins is a relevant brand in the market, and despite continued tough trading conditions we have been able to grow like for like sales, increase transactions and bring more customers through the door, raising the average bottle price in 2010 to just under £8."