Abstract Increasing electrification of final uses can be a viable solution towards low-carbon energy systems, when coupled with local renewable power generation. Mountain areas can already benefit from high shares of hydro-power generation, but, at the same time, rely on oil products for transport and for the heating sector in remote areas where natural gas infrastructures are not available. This research work evaluates potential scenarios for the electrification of transport and heating sectors, by coupling the simulation tool EnergyPLAN with a multi-objective optimization algorithm to analyse economic and environmental aspects. Results show that the largest benefits are expected from the electrification of the heating sector. Indeed, a CO2 emissions reduction up to 30% can be reached by acting on the transport sector alone, while up to 65% combining it with measures on heating, industry and agriculture sectors and additional electricity generation from photovoltaic systems. Moreover, the use of heat pumps can lead to significant CO2 emissions decrease with only to a slight increase in the overall annual costs thanks to lower variable costs that partly compensate the higher required initial investment and electricity storage deployment. The optimization analyses also highlight the effect of progressive penetration of electric vehicles in the private cars fleet and hydrogen trucks in the light-duty vehicles one.