For low‐pressure pervaporation, the performance of spiral wound pervaporation membrane (SWM‐PV) module is significantly influenced by permeate spacer structure. This study addresses mass transport challenges in SWM‐PV modules, focusing on increased gas flow resistance and vacuum attenuation due to membrane envelope deformation in the permeate side channel. Employing fluid and structural simulation models to evaluate phase change and membrane deformation, we successfully optimized SWM‐PV module configurations for improved ethanol recovery. Our strategies included a mass transfer‐enhanced feed spacer to mitigate concentration polarization, a high‐strength permeate spacer to alleviate membrane deformation, and tailored membrane envelopes to balance packing density and mass transfer efficiency. These synergistic optimizations led to a 22.1% improvement in ethanol mass transfer coefficient and a 78.5% reduction in module's specific energy consumption. Our work reveals the importance of permeate spacer structure in optimizing SWM‐PV modules, offering clear guidance for the development of mass transfer‐enhanced SWM‐PV modules.