The broadcaster, which has signed a deal with Disney for the VOD rights in the UK, is running a free promotion on the first two episodes and will charge viewers 99p post-transmission or £1.99 pre-transmission to download the remainder of the series.
Last year, Five became the first broadcaster to launch VOD services, called Five Download, although to date the offering has been limited to the other US hit CSI, comprising CSI: Crime Scene Investigation and its spin-offs, CSI: NY and CSI: Miami.
Five is also exploring offering advertising-funded content on its service, but has said it will concentrate on a paid-for service, plus some sponsorship opportunities, until there is a proven business model.
Last week, Media Week revealed that ITV has delayed the launch of its broadband service, which will include advertiser-funded VOD. Originally slated for the end of the month, the launch has now been put back to May.
Channel 4 is launching advertiser-funded VOD content next month, although it already offers pay-per-view content of its US imports.
Separately, Titan Magazines is to launch an official magazine companion to Grey's Anatomy, featuring interviews with the creators, writers and stars. The first issue goes on sale on 5 April.