The car and bicycle specialist will task West with overseeing all aspects of its online sales, including the Halfords.com website, the delivery process of orders, and its "reserve and collect" service.
West will join the executive management team and report directly to chief executive David Wild, when he joins the business on 5 March.
Halfords has brought in West for the expertise he gained at Asda, where he launched its "click and collect" service and its Home Shopping Centres.
According to Halfords, West helped double the turnover of Asda's online grocery business during his three years in the role.
The specialist retailer has been ramping up its online offer in the last year through the launch of the Halfords app, a new mobile site and the relaunched Halfords Autocentres website.
West's hiring follows Halfords' appointment of former Emap group managing director Claudia Arney to the board as a non-executive director, in order to tap her digital expertise.
Wild said: "Our multichannel offer is a key area of development for the Halfords business. More and more customers are researching and shopping online. Clive's appointment will help us continue to progress in this fast-changing area."
Matthew Chapman at @mattchapmanUK