Four commercial polyvinyl alcohol (PVA) and polydimethylsiloxane (PDMS) membranes were applied to the pervaporation of an azeotropic mixture containing trimethyl borate, a precursor to boronic acids used in Suzuki couplings and a gaseous anti‐oxidant in solder flux or brazing. The degree of cross‐linking of the chains in the active layer played a crucial role in the membrane process using the membranes PERVAP 4155‐80, PERVAP 4155‐40 and PERVAP 4155‐30. PERVAP 4155‐30 reached the best results from all tested membranes; an impressive selectivity with fast permeation was also achieved with the PERVAP 4060 membrane. Methanol preferentially passed through PERVAP 4155‐30, but trimethyl borate was favorably pervaporated from the mixture by PERVAP 6040, due to the diverse affinities of the membranes.