Metcalfe will report to Nick Collard, group marketing and customer director, and will be responsible for leading the development of digital marketing at Morrisons.
The supermarket is gearing up to launch its first e-commerce operation in Warwickshire in January, before expanding to Yorkshire and covering half of the UK by the end of 2014.
Morrison’s is expected to push its fresh food offering as a point of difference from the other big four supermarkets, with its delivery service realised through a £216m tie-up with Ocado.
Metcalfe left eBay earlier this year after just over 12 months in the role, leaving it unclear as to whether she had a job to go to or not.
She joined eBay as its first UK and Ireland marketing director after the company identified it as the fastest-growing market in Europe.
Prior to this, Metcalfe was an interim head of marketing at Sainsbury’s and has previously held senior digital and customer marketing roles at Debenhams, Sainsbury’s, MyWardrobe.com and Cocosa.com.