Abstract This paper presents the projected changes in daytime-nighttime compound heat waves (HWs) (i.e. concurrent occurrence of HWs both in daytime and nighttime) and associated population exposure in China under the shared socioeconomic pathway (SSP)2-4.5 and SSP5-8.5 scenarios based on the Coupled Model Intercomparison Project phase 6 simulations. A comparison with the changes in daytime HWs (i.e. occurring only in daytime) or nighttime HWs (i.e. occurring only in nighttime) is also conducted. The results generally indicate an aggravated risk of compound HWs in China in the future under warmer scenarios. On the national average, the compound HWs are projected to increase persistently toward the end of the 21st century, with larger increase under SSP5-8.5 than that under SSP2-4.5. The greatest changes occur in northwest China and southern China. Compared with the daytime or nighttime HWs, the projected increase of compound HWs is the greatest. Accordingly, the proportion of compound HWs to the total HW events tends to increase and that of daytime HWs tends to decrease toward the end of the 21st century. The substantial increases in the frequency of compound HWs are expected to cause a significant increase in population exposure across the entire country. The projected increase of nationally averaged population exposure is 12.2-fold (7.9-fold) of the current in the mid-century (2046–2065) and further enhances to 16.3-fold (12.4-fold) in the end-century (2081–2100) under SSP5-8.5 (SSP2-4.5). The largest increases are distributed in western China and southern China. These findings raise the necessity and urgency for policy-makers and the public to develop measurements to address compound HW risks.