Chile is currently engaged in an energy transition process to meet ambitious greenhouse gas reductions and improved air quality indices. In this paper, we apply a long-term energy planning model, with the objective of finding the set of technologies that meet strong reductions of CO2 emissions and of local PM2.5 concentrations. For this purpose, we use the existing ETEM-Chile (Energy-Technology-Environment-Model) model which considers a simplified version of the Chilean electricity sector that we extend to the residential and commercial sectors and to local concentration considerations. We propose an original approach to integrate in the same framework local and global emission constraints. Results show that to meet the goal of zero emissions by 2050, electrification of end-use demands increases up to 49.2% with a strong growth of the CO2 marginal cost. It should be noted that this electrification rate is much lower than government projections and those usually found in the literature, in certain geographic areas in southern Chile with a wide availability of firewood for residential heating. Regarding local PM2.5 concentrations, our analysis shows that even without a specific emission reduction target, acceptable PM2.5 concentrations are achieved by 2045, due to first the emergence of more efficient, cleaner and cost-effective end-use technologies, in particular, residential firewood heaters, and second the use of drier and therefore less contaminating firewood. Achieving acceptable air quality as early as 2030 is also possible but comes with a high marginal cost of PM2.5 concentration. Our results illustrate the need for implementing effective public policies to (i) regulate the firewood heating market to increase its production and improve its environmental quality and (ii) incentivize the installation of efficient firewood heaters in the residential sector.