The plan for and implementation of greenhouse gas (GHG) mitigation solutions within an urban area may have co-benefits in local air quality levels. In particular, the use of electricity as the only energy carrier for heating/cooling the building stock (partly or fully powered by rooftop photo-voltaic systems) will lead not only to GHG emissions savings, but also to significant reductions in emissions of air pollutants from small combustion activity. Similarly, electrification of the vehicle fleet is expected to contribute to a cleaner atmosphere over and downwind the road city network. The current study aspires to answer the following question: Which is the quantified impact on intra-urban AQ, when penetration of electrification into the building and/or the road sector(s) is applied in a megapolis of the southeastern Mediterranean? The methodological pathway followed starts with the translation of targeted European and/or National policies (for the transition to climate neutrality and adaptation to climate change) in air pollution emission reduction scenarios. The numerical atmospheric model system WRF/ Episode-CityChem ingests these scenarios towards high-resolution (100 m) air pollution concentrations over the urban area of Athens (Greece) during a baseline year, evaluated against measurements from multiple in situ stations of the National networks. PM2.5 and NO2 improvements through 10 GHG mitigation scenarios are noted at the urban core and over several populated municipalities around the city center. Measures for both sectors ensure impacts for the inner-city center up to − 15% for each of these two pollutants.