To date, few attempts have been made to associate air conditioning behavior with environmental conditions and the occupants’ thermal sensations and physiological states simultaneously. In this study, a series of experiments were conducted in a climate chamber environment, representative of a typical intermittent air conditioning process in residences. For 29 participants, local skin temperatures, thermal sensation and the participants’ intention of turning off air conditioning were recorded continually. Skin temperature and thermal sensation were found to keep decreasing over time, which in turn triggered turning off air conditioning. It is also noted that participants reported different thermal sensations when they intended to turn off air conditioning. However, there was no statistically significant difference in skin temperature of exposed body parts such as foot and calf. Additionally, given the ambient set temperature, the probability of turning off air conditioning exponentially increased with the increasing air conditioning duration. Accordingly, from a physiological perspective, the occupants’ behavior of turning off air conditioning was largely dependent on the local skin temperature of exposed body parts. From an environmental perspective, air conditioning duration demonstrated influences on the air conditioner switch-off. The lower the ambient temperature or the longer the exposure to air conditioning environment, the stronger the intention of the participants to turn off air conditioning.