Air pollution and the urban heat island effect are consistently linked to numerous respiratory and heat-related illnesses. Additionally, these stressors disproportionately impact low-income and historically marginalized communities due to their proximity to emissions sources, lack of access to green space, and exposure to other adverse environmental conditions. Here, we use relatively low-cost stationary sensors to analyze PM2.5 and temperature data throughout the city of Richmond, Virginia, on the ten hottest days of 2019. For both hourly means within the ten hottest days of 2019 and daily means for the entire record for the year, the temperature was found to exhibit a positive correlation with PM2.5. Analysis of hourly means on the ten hottest days yielded a diurnal pattern in which PM2.5 levels peaked in the early morning and reached their minima in the mid-afternoon. Spatially, sites exhibiting higher temperatures consistently had higher PM2.5 readings, with vulnerable communities in the east end and more intensely developed parts of the city experiencing significantly higher temperatures and PM2.5 concentrations than the suburban neighborhoods in the west end. These findings suggest an uneven distribution of air pollution in Richmond during extreme heat events that are similar in pattern but less pronounced than the temperature differences during these events, although further investigation is required to verify the extent of this relationship. As other studies have found both of these environmental stressors to correlate with the distribution of green space and other land-use factors in cities, innovative and sustainable planning decisions are crucial to the mitigation of these issues of inequity going forward.