To move towards environmentally-sustainable transport systems, electric vehicles (EVs) are increasingly seen as viable alternatives to internal combustion vehicles (ICVs). To ensure effectiveness of such deployment, holistic assessments of environmental impacts can help decision-makers determine optimised urban strategies in a long-term perspective. However, explicit guidance and conduct of such assessments are currently missing. Here, we therefore propose a framework using life cycle assessment that enables the quantification of environmental impacts of a transport system at full urban scale from a fleet-based, foresight perspective. The analysis of the passenger car fleet development in the city of Copenhagen for the years 2016-2030 is used as a proof-of-concept. We modelled and compared five powertrain technologies, and we assessed four fleet-based scenarios for the entire city. Our results showed relative environmental benefits from range-extended and fuel-cell EVs over ICVs and standard EVs. These results were found to be sensitive to local settings, like electricity grid mix, which could alter the relative environmental performances across EV technologies. The comprehensive framework developed here can be applied to other geographic areas and contexts to assess the environmental sustainability of transport systems.