An Extended Decomposed Theory of Planned Behaviour (DTPB) is developed that integrates emotions towards car driving and electric cars as well as car driving habits of the DTPB, and is empirically validated in a Belgian sample (n = 1023). Multi-group comparisons explore how the determinants of usage intention are different between groups of consumers differing in environmentally-friendly behaviour, environmental concern, innovativeness and personal values. Besides attitudes, media, perceived complexity, compatibility and relative advantage, emotions towards the electric car and reflective emotions towards car driving have a strong effect on usage intention. Car driving habits and perceived behavioural control (facilitators and constraints) do not substantially affect usage intention. Only people differing in personal values show a different motivational structure for a number of important drivers of usage intention.