Currently, many cities in Europe are affected by concentrations of PM2.5 and NO2 above the WHO guidelines on the protection of human health. This is a global problem in which the growth of road transport constitutes a major factor. Looking to the future, electric vehicles (EVs) are considered to be the choice technology for reducing road transport greenhouse gas emissions, but their impact on air quality needs to be considered. Taking the UK as a case study, this paper begins by understanding the trajectory of a future scenario without the introduction of EVs, reflecting on the latest emission control improvements in internal combustion engine vehicles (ICEVs). This is then compared to a 2050 scenario in which the introduction of EVs, based on the UK government’s Transport Decarbonisation Plan, is reviewed. This plan includes a ban on the sale of ICEV cars and LGVs, beginning in 2030, with the subsequent electrification of heavier vehicles. By 2030, population exposure to NOx was found to be significantly reduced in the ICEV scenario, with a marginal further reduction found for the EV scenario. The EV scenario further reduced NOx exposure by 2050, with most of the benefits being realized before 2040. For the ICEV and EV scenario, PM2.5 emissions were largely unchanged due to the primary contribution of non-exhaust emissions, suggesting that EVs are likely to yield relatively smaller changes in exposure to PM2.5 than for NOx.