We made static and personal PM2.5 measurements with a miniature monitor (RTI MicroPEM) to characterise the exposure of women cooking with wood and charcoal in indoor and outdoor locations in rural Malawi, together with measurements of blood pressure and peak expiratory flow rate (PEFR). Mean PM2.5 concentrations of 1338 and 31 µg/m3 were observed 1 m from cookstove locations during cooking with wood and charcoal, respectively. Similarly, mean personal PM2.5 exposures of 706 and 94 µg/m3 were observed during cooking with wood and charcoal, respectively. Personal exposures to PM2.5 in indoor locations were 3.3 and 1.7 times greater than exposures observed in equivalent outdoor locations for wood and charcoal, respectively. Prior to the measured exposure, six out of eight participants had PEFR observations below 80% of their expected (age and height) standardised PEFR. We observed reductions in PEFR for participants cooking with wood in indoor locations. Five out of eight participants reported breathing difficulties, coughing, and eye irritation when cooking with wood but reported that symptoms were less severe when cooking with charcoal. In conclusion, we observed that exposure to PM2.5 was substantially reduced by cooking outdoor with charcoal. As both wood and charcoal fuels are associated with negative environmental and health impacts, the adoption of high-efficiency cookstoves and less polluting sources of energy will be highly beneficial. Cooking outside whenever possible, and minimising the time spent in close proximity to stoves, may be simple interventions that could reduce the risks of exacerbation and progression of respiratory and cardiovascular diseases in Malawi.