The deal comes a week after the retailer defended its £8m sponsorship of the Hit 40 UK chart show in the wake of an 11% audience slide.
It sees Woolworths take over sponsorship of the show from Megabowl, which backed the inaugural National Music Awards show last year.
The ceremony was staged at the Carling Hammersmith Apollo on October 26. ITV1 will provide three hours of peak-time coverage of the awards on November 12. The show will be repeated on ITV2 at a later date.
Actress Amanda Holden hosted the awards, which were voted on by the public.
There were live performances from artists such as Gareth Gates, Girls Aloud and The Cheeky Girls.
Gates won the favourite male singer award, Rachel Stevens was voted favourite female singer and Coldplay won the most popular band award.
Sponsorship credits were created for Woolworths by Bartle Bogle Hegarty.
The deal was negotiated between Granada Enterprises and Alliance, the sponsorship division of ZenithOptimedia.