Abstract Abstract Window operation is not only an important method for improving the indoor thermal environment and air quality, but also a significant way to reduce energy consumption of air-conditioned rooms during off-running periods in transition seasons. The occupants' window-operation behavior is influenced by both objective factors, such as thermal comfort and indoor air quality; and objective sensation, such as psychology and physiology, introducing considerable randomness and uncertainty. A two-month field observation of occupant window-opening behaviors for natural ventilation in an office building during the transition seasons was carried out in Chongqing, China. Multi-factor analysis of variance was conducted in data analysis using SPSS statistical software. The results showed that outdoor air temperature significantly affected window opening among other factors such as outdoor relative humidity, indoor air temperature, indoor relative humidity, and indoor CO2 concentration, which have much less effect. The main trigger point for opening windows in the transition seasons is from occupants' desire to improve the indoor thermal and air quality environment. A probability model of occupants' window operation was proposed based on logistic regression analysis. Meanwhile, the Monte Carlo simulation results indicate that during transition seasons (when outdoor temperature varied from 15 to 30 °C), the probability of window opening in office buildings follows a normal distribution and increases linearly along with the outdoor temperature growth.