The pop star makes his acting debut in the ad, in which he is interviewed by Woolworths' sheep and sheepdog characters, Wooly and Worth, on "Woolworths News".
The spot, called "ladies' man", sees Ward quizzed over whether being a hit with women has caused him any difficulties.
The commercial, which plugs the forthcoming release of Ward's debut album, breaks on Easter Saturday as part of a TV, press, in-store and digital campaign from the retailer.
Woolworths last used celebrities in its advertising in 2002, when it ran an ad featuring the comedian Paul Kaye, best known for his Dennis Pennis character.
The Woolworths marketing director, Stephen Robertson, said: " Shayne Ward is currently the hottest property in this country and our ad team has pulled off a major coup."
Ward is also reported to have signed a £500,000 deal with Calvin Klein to feature in a series of US press and TV ads for the fashion designer.