Ecuador presents a unique case study for evaluating personal air pollution exposure in a middle-income country where a clean cooking fuel has been available at low cost for several decades. We measured personal PM2.5 exposure, stove use, and participant location during a 48-h monitoring period for 157 rural and peri-urban households in coastal and Andean Ecuador. While nearly all households owned a liquefied petroleum gas (LPG) stove and used it as their primary cooking fuel, one-quarter of households utilized firewood as a secondary fuel and 10% used induction stoves secondary to LPG. Stove use monitoring demonstrated clear within- and across-meal fuel stacking patterns. Firewood-owning participants had higher distributions of 48-h and 10-min PM2.5 exposure as compared with primary LPG and induction stove users, and this effect became more pronounced with firewood use during monitoring.Accounting for within-subject clustering, contemporaneous firewood stove use was associated with 101 μg/m3 higher 10-min PM2.5 exposure (95% CI: 94–108 μg/m3). LPG and induction cooking events were largely not associated with contemporaneous PM2.5 exposure. Our results suggest that firewood use is associated with average and short-term personal air pollution exposure above the WHO interim-I guideline, even when LPG is the primary cooking fuel.