Pervaporation and vapor-phase membrane separation methods for the recovery of bioalcohols from dilute aqueous solutions have been critically compared. The importance of taking into account the liquid-vapor equilibrium diagram in studies on the separation of binary aqueous-alcoholic liquid media by these methods has been shown. Previously published experimental data on the transport of water, ethanol, and n-butanol vapors in hydrophobic membranes based on the glassy polymers poly(vinyltrimethylsilane) (PVTMS), poly(1-trimethylsilyl-1-propyne) (PTMSP), and poly(4-methyl-1-pentyne) (PMP) have been analyzed. Schemes of butanol and ethanol recovery by the vapor-phase membrane separation process from fermentation broths for the cases of application of water-selective and alcohol-selective membranes have been presented, as well as the results of mathematical simulation of the process and assessment of energy consumption.