Superfast broadband is available to 73% of UK households; however, Ofcom's scorecard found that less than a fifth had adopted the service.
The UK also scored highest in terms of the proportion of people who have bought goods online over a year (77%).
Communications minister Ed Vaizey said: "The government's roll-out of superfast broadband is accelerating - Britons already do more business online than any other European country, and the news that we now have the best superfast coverage of all five leading European economies is testament to the progress made to date."
While the UK may lead in broadband speeds among the five largest economies in Europe, Boris Ivanovic, chairman and founder of Hyperoptic, a provider in FITH broadband said: "The overall conclusion that the UK has the best broadband in Europe is highly questionable, as broadband infrastructure in other European countries - especially in Scandinavia - is far superior to ours at the moment."
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