Global warming has led to the enhancement of diurnal (daytime-nighttime) compound heat waves, which can severely affect the population’s physical health and productive life; this is particularly the case for vulnerable populations that are more susceptible to psychological and physiological harm with the future normalization of heatwave scenarios. In this study, we attributed the changes in population exposure under diurnal compound high temperatures (HTs) and extremely high temperatures (EHTs) to the influence of climatic (exposure duration) and population factors and their combined influence to determine the relationship between exposure duration and the changes in exposure of vulnerable populations. Diurnal compound HT and EHT covered a land area of 4,016,800 and 1,984,200 km2, respectively. The heat-exposed area spread step-like in all directions, centering on the 24-h high-exposure area with a strong gradient effect. The area of prolonged exposure shifted from the Yellow-Huai-Huai Plain across the geographical boundary between the south and the north to the middle and lower reaches of the Yangtze River Plain. Meanwhile, the average maximum value of vulnerable population exposure reached 186,800 and 93,100 person-h, with high values in Zhengzhou, Chongqing, Wuhan, Chengdu, Beijing, and other cities. Changes in vulnerable population exposure were dominated first by demographic factors and then by climatic factors, with the dominance of climatic factors evident in areas of prolonged exposure. Under prolonged exposure to daytime-nighttime compound EHT, changes in the exposure of child and older populations were dominated by climatic factors with a contribution rate of 87.16% and 87.43%, respectively. Therefore, suitable cooling measures should be proposed for vulnerable populations under prolonged exposure, focusing more on the physical and mental health of children and older adults exposed to compound EHT.