This work analyses the potential air quality improvements resulting from three fleet electrification scenarios (∼13, 26 and 40%) by replacing conventional vehicles with Electric Battery Vehicles (EBVs), Plug-in Hybrid Electric Vehicles (PHEVs) and Hybrid Electric Vehicles (HEVs). This study has been performed for the cities of Barcelona and Madrid (Spain), where road transport is the primary emission source. In these urban areas, several air quality problems are present, mainly related to NO2 and particulate matter. The WRF-ARW/HERMESv2/CMAQ model system has been applied at high spatial (1 × 1 km2) and temporal (1 h) resolution. The results show that fleet electrification offers a potential for emission abatement, especially related to NOx and CO. Regarding the more ambitious scenario (∼40% fleet electrification), reductions of 11% and 17% of the total NOx emissions are observed in Barcelona and Madrid respectively. These emissions reductions involve air quality improvements in NO2 maximum hourly values up to 16%: reductions up to 30 and 35 μg m−3 in Barcelona and Madrid, respectively. Furthermore, an additional scenario has been defined considering electric generation emissions associated with EBVs and PHEVs charging from a combined-cycle power plant. These charging emissions would produce slight NO2 increases in the downwind areas of <3 μg m−3. Thus, fleet electrification would improve urban air quality even when considering emissions associated with charging electric vehicles. However, two further points should be considered. First, fleet electrification cannot be considered a unique solution, and other management strategies may be defined. This is especially important with respect to particulate matter emissions, which are not significantly reduced by fleet electrification (<5%) due to the high weight of non-exhaust emissions. Second, a significant introduction of electric vehicles (26–40%) involving all vehicle categories is required to improve urban air quality.