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The development of high speed rail (HSR) in the UK has generated a lively debate over a number of issues regarding its benefits to the economy and the environment. This study aims to provide more clarity over one such issue; the CO2 emissions saving that can be achieved from a shift away from domestic air travel to use of HSR. Four routes were chosen for analysis: London Heathrow to Leeds, Manchester, Edinburgh and Glasgow. CO2 emission calculations take into account a number of scenarios representing the possible situation in 2033, when HSR services to Leeds and Manchester are due to start operating. Results show that there is a significant potential to reduce CO2 where all the passengers on these routes switch to using HSR instead of air services, with the medium scenario showing a 97.3% decrease in emissions from such a shift. It is proposed that this would be possible with a new business model being introduced by airlines in which they provide the same connecting services to Heathrow, but replacing aircraft with the HSR service. This study also highlights that the issue of a modal shift from air travel to HSR is more complex than just making a simple comparison. It is acknowledged that there are also a number of other issues that need to be taken into account, such as the lack of large scale technological solutions being available for aircraft and energy security issues that could potentially affect important links between cities in the future.