The union hopes to secure collective bargaining rights at 20 of the retailer's distribution centres and payment of the 2005 bonus and safe work rates.
The decision followed failed talks between GMB general secretary Paul Kenny and Asda boss Andy Bond. The grocer said Kenny had walked out of the most recent meeting.
A ballot of 25,000 members was authorised in February originally. However, after a meeting with the supermarket on April 11, the union withdrew its intention to strike. A joint statement was issued saying both groups had agreed to work together to form a National Joint Council for distribution.
But since then relations between the two have collapsed.
Jude Brimble, GMB National Officer for GMB members working at Asda, said: 'The GMB have spent more than 20 hours in talks with the company to try and find a satisfactory resolution. We thought we had made progress, but in the end we are back to square one.'
In a statement, Asda said it was under the impression significant steps forward had been made at the first meeting and is disappointed that this is no longer the case.
Asda people director Caroline Massingham said: 'Sadly, we can't do this on our own and it seems the GMB are no longer prepared to work with us. It's become clear that they have gone back on our agreement and, once again, only seem interested in threatening us with industrial action. We think our colleagues deserve better than to be wrapped up in a 1970s-style industrial bargaining dispute and if the GMB are serious about a genuine dialogue, they only have pick up the phone.'
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