Heat exposure for urban populations has become more prevalent as the temperature and duration of heat waves in cities increase. Occupational exposure to heat is a major concern for personal health, and excessive heat exposure can cause devastating outcomes. While occupational heat exposure studies have traditionally focused on environmental temperature, work intensity, and clothing, little is known about the daily exposure profile of workers, including their daily travel and working patterns. This study developed a novel measure of exposure and reprieve dynamics, the moving average hourly exposure (MAHE) to balance short-duration but high-exposure events and capture the inability to reprieve from exposure events. MAHE was assessed by combining an activity-based travel model (ABM) and the Occupational Requirement Survey to simulate urban workers' total daily heat exposure. The simulation considers daily travel, work schedules, and outdoor working frequency. The simulation was conducted for 1 million workers in Phoenix, Arizona, using Mean Radiant Temperature (MRT). The results show that 53% to 89% of workers in Phoenix's construction, agriculture, transportation, raw material extraction, and entertainment industries will likely experience MAHE over 38°C for at least an hour. These industries also have up to 34% of the laborers exposed to over 7 hours of continuous 38°C and above MAHE exposure. The location of the most intense heat exposure was identified near the downtown and central business districts, significantly different from the home locations of the workers in suburban and rural areas. Formulating the MAHE balances heat risk events with cooling benefits and aids in identifying individuals with prolonged high heat exposure.