Urban outdoor space has a very important impact on the quality of people’s outdoor activities, which has influenced people’s health and moods. Its influence is the result of the combined action of various factors. Thermal and air quality environment are important factors affecting the overall comfort of the urban outdoor space. At present, there are few research on interaction with thermal and air quality environment. Therefore, a meteorological measurement and questionnaire survey have been conducted in a representative open space in a campus in Xi’an, China. The following are the research results:(1) Mean physiological equivalent temperature (MPET) is a significant factor affecting thermal sensation vote (TSV) and thermal comfort vote (TCV). PM2.5 has no significant effect on thermal comfort vote (TCV), but it is a considerable factor affecting thermal sensation vote (TSV) when 10.2°C ≤ MPET<21°C (P = 0.023 *). (2) PM2.5 is a significant factor affecting air quality vote (AQV) and breathing comfort vote (BCV).Mean physiological equivalent temperature (MPET) has no significant impact on air quality vote (AQV), but it is a considerable factor affecting breathing comfort vote (BCV) when 10.2°C ≤ MPET<21°C (P = 0.01 **). (3) Mean physiological equivalent temperature (MPET) is a significant factor affecting overall comfort vote (OCV), but PM2.5 is not. In general, When 10.2°C ≤ MPET<21°C (-0.5 < -0.37 ≤ TCV ≤ 0.12 <0.5), the interaction between thermal and PM2.5 environment is significant on thermal sensation vote (TSV) and breathing comfort vote (BCV). This study can provide experimental support for the field of multi-factor interaction, which has shown that improving the thermal environment can better breathing comfort, while reducing PM2.5 concentration can promote thermal comfort. And can also provide reference for the study of human subjective comfort in urban outdoor space in the same latitude of the world.