A Pd-doped organosilica membrane based on bis(triethoxysilyl)ethane is successfully developed by the polymeric sol–gel method. Its microstructure, chemical composition, and separation performance are compared with those of the undoped organosilica membrane. Gas adsorption analysis indicates that the Pd-doped organosilica membrane has larger micropores compared with the undoped organosilica membrane. The gas permeation results show that the Pd-doped organosilica membrane has much higher gas permeances than the undoped organosilica membrane due to the enlarged micropores after Pd-doping. The Pd-doped organosilica membrane also exhibits a significantly improved hydrothermal stability. The enhanced hydrothermal stability can be explained by the mechanism that Pd particles act as inhibitors and prevent the formation of mobile silica groups (e.g., Si–OH) under steam condition. Metal-doping (e.g., Pd-doping in this work) may offer a new approach to develop high performance membranes with enhanced gas permeances and hydrothermal stabilities in gas separation applications.