Morley, 33, will oversee the retailer's £27m ad budget as it demerges from parent Kingfisher. She was promoted to the role last week following a year-long stint as head of clothing for Woolworths.
Morley takes over marketing responsibilities from Ken Lewis, Kingfisher's commercial director.
Lewis was formerly marketing director, having taken over from Alan McWalter, who left for Marks & Spencer in September 1999. The appointment comes in the week Woolworths shares floated on the stock exchange, following the demerger.
As well as supervising the retailer's brand advertising, handled by Bates UK, Morley will focus on brand strategy and positioning. She said: "My brief is to clarify our retail proposition in local stores. I will look at our current plans and priorities and work on refining them.
Morley's immediate focus will be on this year's pre-Christmas activity. This is likely to be followed by a wide-ranging review of Woolworths' marketing, in conjunction with agencies Bates UK and Zenith Media.
The retail chain also works with Storm, part of the Triangle Communications group. Morley said that Woolworths would continue to work with all its current agencies.
Morley, who has yet to be replaced as head of clothing, joined Woolworths last year following spells as managing director of home shopping and business unit director for home and leisure at Asda. She has also worked at fashion re-tailer Laura Ashley as buying and merchandising director.
Woolworths' flotation has been a rocky process, following reports of boardroom disagreements over former Railtrack chief Gerald Corbett's chairmanship of the company.