The comfort level of outdoor thermal environments is affected by several factors. Previous studies of thermal comfort have generally investigated the main microclimatic factors as dependent variables, such as the temperature, wind speed, humidity, and thermal radiation, but the influence of the air quality has rarely been explored. In this study, we acquired meteorological element observations and conducted questionnaire surveys in Peach Blossom Park, Hebei University of Technology, and Xigu Park in Tianjin. We analyzed the effects of the outdoor air quality and thermal environment on the thermal comfort in order to provide a theoretical basis for comprehensive evaluations of the outdoor environment and the mechanism. The results showed that thermal resistance of clothing and ambient temperature followed a negative step change, where people generally reduced the minimum amount of clothing when the temperature exceeded 28 °C. One unit change in the thermal sensation vote (TSV) occurred for every 11 °C rise in the physiological equivalent temperature (PET). The neutral PET was 21.68 °C, and the comfortable PET was about 23 °C. The air quality index (AQI) and air satisfaction were negatively correlated, and satisfaction decreased by 1 unit for every change of 230 AQI. The transitional season was most comfortable when the temperature felt slightly cool (TSV = −0.70). The neutral TSV was 0.507 in the summer and −0.334 in the winter. Air quality had a significant effect on the thermal comfort vote (TCV) (p = 0.0485 < 0.05). The effect of PET on TCV was highly significant (p < 0.01).