Residential firewood burning is the main source of PM2.5 emissions in southern and central Chile. In Chile, approximately 4000 premature deaths are observed each year due to air pollution. Mitigation policies aim to reduce dwellings' energy demand and foster cleaner but more expensive energy sources. Pre-existing energy poverty conditions are often overlooked in these policies, even though they can negatively affect the adoption of these measures. This article uses southern and central Chile as a case study to assess quantitatively different policy scenarios of PM2.5 emissions between 2017 and 2050, considering energy poverty-related effects. Results show that PM2.5 emissions will grow 16% over time under a business as usual scenario. If thermal improvement and stove/heater replacements are implemented, PM2.5 reductions depend on the scale of the policy: a 5%–6% reduction of total southern and central Chile PM2.5 emissions if only cities with Atmospheric Decontamination Plans are included; a 54%–56% reduction of PM2.5 emissions if these policies include other growing cities. Our study shows that the energy poverty effect potentially reduces the effectiveness of these measures in 25%. Consequently, if no anticipatory measures are taken, Chile's energy transition goals could be hindered and the effectiveness of mitigation policies to improve air quality significantly reduced.