Polyvinyl alcohol (PVA) pervaporation (PV) membranes have been extensively studied in the field of ethanol dehydration. The incorporation of two-dimensional (2D) nanomaterials into the PVA matrix can greatly improve the hydrophilicity of the PVA polymer matrix, thereby enhancing its PV performance. In this work, self-made MXene (Ti 3 C 2 T x -based) nanosheets were dispersed in the PVA polymer matrix, and the composite membranes were fabricated by homemade ultrasonic spraying equipment with poly(tetrafluoroethylene) (PTFE) electrospun nanofibrous membrane as support. Due to the gentle coating of ultrasonic spraying and following continuous steps of drying and thermal crosslinking, a thin (~1.5 μm), homogenous and defect-free PVA-based separation layer was fabricated on the PTFE support. The prepared rolls of the PVA composite membranes were investigated systematically. The PV performance of the membrane was significantly improved by increasing the solubility and diffusion rate of the membranes to the water molecules through the hydrophilic channels constructed by the MXene nanosheets in the membrane matrix. The water flux and separation factor of the PVA/MXene mixed matrix membrane (MMM) were dramatically increased to 1.21 kg·m -2 ·h -1 and 1126.8, respectively. With high mechanical strength and structural stability, the prepared PGM-0 membrane suffered 300 h of the PV test without any performance degradation. Considering the promising results, it is likely that the membrane would improve the efficiency of the PV process and reduce energy consumption in the ethanol dehydration.