The variability of daytime–nighttime compound heat waves (CHWs) is a highly concerning issue due to severe impacts on human and natural systems. Although several studies surveyed physical processes for the CHW occurrence, its interannual variability and associated mechanisms have not been well understood. Focusing on CHWs in the Yangtze River valley (YRV, a hotspot across China), this paper indicates an emergence of enlarged interannual variability after entering into the twenty-first century, before which the interannual variability was quite small. The possible mechanism underlying the high interannual variability is further explored in terms of atmospheric and oceanic backgrounds. The results show that the atmospheric background associated with higher-than-normal CHWs over the YRV features anticyclonic circulation anomalies tilting southeastward from the north of the YRV in the upper troposphere to the western Pacific in the lower troposphere. Accordingly, the upper-tropospheric easterly and lower-tropospheric southwesterly anomalies dominate the YRV, causing anomalous subsidence and increased humidity in situ, respectively, which benefit the increase in CHWs. The tripole (positive–negative–positive) sea surface temperature (SST) anomalies in the North Atlantic (NA) and the positive SST anomalies in the Maritime Continent (MC) also play roles in increasing the YRV CHWs by influencing the above atmospheric circulations. The NA tripole SST anomalies tend to affect the upper- and midtropospheric anticyclonic anomalies through the eastward-propagating wave train across Eurasia. The warming of the MC SSTs can impact the lower-tropospheric anticyclonic anomaly over the western Pacific via local meridional circulation. The opposite situations are applicable for decreased CHWs over the YRV.