This paper investigates the extreme wet‐bulb temperatures (TWs) in China, with a focus on understanding the relative contributions of temperature and moisture to the extremes. Analysis of station observations shows that daily extreme temperatures (T), specific humidity (q), and TWs generally co‐occur in Southeastern China, while extreme TW and T rarely overlap in the arid and semiarid North and Northwest China. Overall, q contributes more than T to extreme TWs, especially in North and Northwest China. Based on the relative contributions of q and T, regional extreme TW events are classified as q dominated and T dominated, respectively, to study their large‐scale environment. Cluster analysis of global reanalysis data shows that extreme TWs are generally accompanied by increased surface air temperature and humidity, concomitant with anomalous high pressure, and notable water vapor flux convergence. However, important differences are also seen in the large‐scale environment during q‐dominated and T‐dominated extreme TWs. During q‐dominated extreme TWs, the large‐scale environment favors convection, as indicated by ascending motions, decreased downward solar radiation as well as increased precipitable water and near‐surface relative humidity. In contrast, during T‐dominated extreme TWs, convection is inhibited by the large‐scale environment that features descending motion and increased downward solar radiation, decreased precipitable water, and decreased relative humidity. Consistent with the contrasting environments, we demonstrate that T‐dominated extreme TWs tend to last longer than q‐dominated extremes. Given the significant role of moisture in extreme TWs, more research is needed to understand its impacts on heat stress now and in the future.