The site is in English, with the initial aim of targeting expats but with foreign language sites planned for later this year.
There will be a flat delivery charge of five euros and products will be shipped in seven days. Littlewoods is offering a special incentive for a limited period: free postage and packaging to Spain, Germany, France and Portugal on customers' first orders over 50 euros.
Shop Direct's push into continental Europe caps a summer of activity for the UK's biggest home shopping firm, which saw a push into a younger, more internet-savvy market.
Two months ago Shop Direct relaunched Woolworths as an online brand catering for children's clothes, toys and party materials.
In June, Shop Direct Group rebranded Littlewoods Direct as Very, with a new website very.co.uk, to appeal to a younger online customer base.
Mark Newton-Jones, Shop Direct's chief executive, said Littlewoods Europe was in response to customers demand for a European online offer for Littlewoods products.
Littlewoods Europe is aimed at women and young families, will sell more than 250 high street brands, including Levi's, Puma, Nike, Birkenstock and Firetrap, as well as own label brands such as Goodsouls.
Its core categories are clothing, footwear, toys, children's wear, homeware, DVDs and CDs.
An interview with Newton-Jones in the in March quoted Shop Direct as having 10.5m customers on its database, about half of which have made a purchase in the past 12 months.
Shop Direct is the UK's largest online and home shopping retailer with annual sales of £1.6 billion.
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