Extracting ethanol by steam directly from fermented solid-state bagasse is an emerging technology of energy-efficient bioethanol production. With continuous solid-state distillation (CSSD) approach, the vapor with more than 25 wt% ethanol flows out of the column. Conventionally, the vapor was concentrated to azeotrope by rectification column, which contributes most of the energy consumption in ethanol production. As an alternative, a process integrating CSSD and vapor permeation (VP) membrane separation was tested. In light of existing industrial application of NaA zeolite hydrophilic membrane for dehydration, the prospect of replacing rectification operation with hydrophobic membrane for ethanol enriching was mainly analyzed in this paper. The separation performance of a commercial PDMS/PVDF membrane in a wide range of ethanol–water-vapor binary mixture was evaluated in the experiment. The correlation of the separation factor and permeate flux at different transmembrane driving force was measured. The mass and energy flow sheet of proposed VP case and rectification case were estimated respectively with process simulation software based on experimental data. Techno-economic analysis on both cases was performed. The results demonstrated that the additional VP membrane cost was higher than the rectification column, but a lower utilities cost was required for VP. The discount payback period of supplementary cost for VP case was determined as 1.81 years compared with the membrane service lifetime of 3 years, indicating that the hybrid CSSD-VP process was more cost effective and energy efficient.