Advertising will run on teen web sites and chatrooms until the end of March, and a dedicated web site (www.thinkuknow.com) has been redeveloped.
The campaign will also feature television for the first time, as the Home Office tries to reach an audience of teenage boys, who are not reached as easily as girls through other media.
The commercial, which has previously run in cinemas, was created by ad agency Ogilvy & Mather. It demonstrates how easy it is for anyone to claim to be someone else on the internet. It features a voiceover by a teenager, but lip-synched by an older man.
Home Office minister Hilary Benn said: "We are aware of the potential for paedophiles to misuse modern technology to abuse the trust children place in them by attempting to 'groom' them through chatrooms."
The Government claims that a similar campaign last year resulted in an 11 per cent increase in awareness not to give out personal information online and a 12 per cent increase among parents of awareness of safety measures for children who surf the internet.
The ads will appear on TV and radio until the end of January.
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