Wet compression is widely used to reduce compression work and improve efficiency in gas turbines. However, wet compression has not been industrially applied in the compressed air energy storage system (only few studies on isothermal compressed air energy storage system exist), which has an urgent demand to reduce the compression work. The high-pressure section of the compressed air energy storage system usually contains supercritical air, and the influence of supercritical wet compression is not yet clear. Thus, in this study, supercritical wet compression was numerically investigated in a centrifugal compressor used for the compressed air energy storage system, and its effects on performance and internal flow were also studied. The results show that the ideal maximum evaporation of water droplets in supercritical air is very low, which limits the maximum available water injection ratio; however, wet compression still has some benefits, such as increasing the total pressure ratio and isentropic efficiency and reducing the compression specific work. Moreover, wet compression reduces the diffuser loss but raises the wake loss in the impeller at the near-stall point. For this compressor, the optimum water injection ratio is 0.3%, which reduces the specific work by 0.65% at the designed pressure ratio.