With rail travel largely seen to be a more sustainable method than road-based transport, this paper examines the market segments amongst existing motorists that would be most likely to travel by train in the UK. The analysis is based on a large survey in London and the south-east of England, the area surrounding the routes operated by the train company First Capital Connect. Findings show that train travellers tend to be middle-aged and of a higher social grade, typically taking commuting or business trips. Individuals living within four miles of a station are considerably more likely to travel by rail than those further away. Given the competition from road-based transport, it is of particular interest that the measure highlighted to increase rail use for those living further away from the rail network is to enhance car parking at train stations.