In this study, we apply a latent class choice modelling approach to the employees of the European Investment Bank and the Court of Justice of the European Union in Luxembourg to investigate commuting mode choice behaviour by incorporating individual preference heterogeneity. We found a two-segment preference differentiation of mode choice behaviour determined by their household locations, attitudes towards transport modes as well as their socio-demographic characteristics. Validity and overall goodness-of-fit are compared with a conditional multinomial Logit model. The empirical study confirmed that travel time and the availability of free parking are the two major determinants for Luxembourg residents with respect to their commuting trips by car. The sensitivity analysis indicates that reducing travel time in public transport could be an efficient way to shift car users towards public transport. The results provide useful insights to evaluate the effect of determinants on individual commuting mode choice behaviour for different preference groups.