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In this work, we performed recovery of ethanol from a fermentation broth of banana pseudostem by pervaporation (PV) as a lower‐energy‐cost alternative to traditional separation processes such as distillation. As real fermentation systems generally contain by‐products, it was investigated the effects of different components from the fermentation broth of banana pseudostem on PV performance for ethanol recovery through commercial flat sheet polydimethylsiloxane (PDMS) membrane. The experiments were compared to a binary solution (ethanol/water) to determine differences in the results due to the presence of fermentation by‐products. A real fermented broth of banana pseudostem was also used as feed for the PV experiments. Seven by‐products from fermented broth were identified: propanol, isobutanol, methanol, isoamyl alcohol, 1‐pentanol, acetic acid, and succinic acid. Moreover, the residual sugar content of 3.02 g/L1 was obtained. The presence of methanol showed the best results for total permeate flux (0.1626 kg·m−2·h−1) and ethanol permeate flux (0.0391 kg·m−2·h−1) during PV at 25°C and 3 wt% ethanol, also demonstrated by the selectivity and enrichment factor. The lowest total fluxes of permeate were observed in the experiments containing the acids. Better permeance of 0.1171 from 0.0796 kg·m−2·h−1 and membrane selectivity of 9.77 from 9.30 were obtained with real fermentation broth than with synthetic solutions, possibly due to the presence of by‐products in the multicomponent mixtures, which contributed to ethanol permeation. The results of this work indicate that by‐products influence pervaporation of ethanol with hydrophobic flat sheet membrane produced from the fermented broth of banana pseudostem. [ABSTRACT FROM AUTHOR]