Background: Air pollution has become a major environmental health risk factor, notably in China. Air pollution potentially has the impact of human populations’ health behavior. Gaps in scientific literature remain regarding more accurately estimates the relationship between air pollution and sedentary behavior in China. The purpose of this study is to examine the association between hourly air pollution AP on hourly physical activity (PA) and sedentary behavior (SB) among college students in Beijing, China. The secondary aim was to examine such associations varied at specific times. Methods: A total of 340 participants were recruited from the Tsinghua University, in Beijing, China. Accelerometers provided PA measures, including moderate-to-vigorous physical activity (MVPA), walking steps, energy expenditure and sedentary time for 7 consecutive days. Corresponding AP data by the Beijing Municipal Ecological Environment Bureau in the closed site (Wan Liu site) at Tsinghua University were collected to include average hourly air quality index (AQI) and PM2.5 (µg/m³). Associations were estimated using linear individual fixed-effect regressions.Results: A one level increase in hourly air quality index (AQI) was associated with a reduction in one-hour MVPA by 0.083 minutes (95% CI =[-0.137, -0.029]), 8.8 walking steps (95% CI = [-15.0, -2.6]), and 0.65 kcals of energy expenditure (95% CI =-[1.03, -0.27]). A 10µg/m³ increase in AP concentration in hourly PM2.5 was associated with a reduction in one-hour MVPA by 0.021 minutes (95% CI = [-0.033, -0.010]), 2.2 walking steps (95% CI = [-3.5, -0.9]), 0.170 kcals of energy expenditure (95% CI = [-0.250, -0.089]), and an increase in one-hour SB by 0.045 (95% CI = [0.005, 0.0845]). At a specific time, there are stronger negative associations of AQI and PM2.5 to PA at 8 am, 4 pm, 5 pm and 7 pm. Similarly, stronger positive associations were found at one hour AQI and PM2.5 with SB at 8 am, 9 am, 11 am, and 7 pm. Conclusions: AP may discourage PA and increases SB among freshman students living in Beijing, China. The impact of AP on PA and sedentary behavior at a specific time may be different.