In their continuous battle against congestion and pollution, governments nowadays promote rail as an environmentally friendly Single Occupant Vehicle (SOV) alternative. For comparison, the energy consumption per person kilometre for rail is 0.14 kWh/pkm while that for a car is 0.48 kWh/pkm (Boussauw and Witlox 2009), and electric trains have no direct emissions of air pollutants like PM 10 and NO x. Modal shift policies often target the daily commute since home to work travel is concentrated in the congested peak hours and commuters' travel behaviour is more regular. This regular character seems to fit well with the scheduled nature of rail, and the central location of railway stations fits with the relative concentration of jobs in congested cities (Riguelle, Thomas, and Verhetsel 2007). Furthermore, both cities and public transport are predominant in the sustainable mobility paradigm (Banister 2008). Therefore, the location of jobs in city-regions and the link with rail use, are at the core of our analysis. Besides environmental objectives, employment concerns motivate governments to invest in railways. Indeed, rail can keep jobs in city centres accessible. This indicates that rail can contribute to all three dimensions of sustainability and sustainable transport, the environmental, the social and the economic dimension (Boschmann and Kwan 2008).