As a promising technique for multiphase catalytic reactions, the widespread applications of gas–liquid– solid microreactors are still limited by poor durability. Hence, in this work a novel catalytic membrane was synthesised for carrying out the hydrogenation reaction of a bio-oil model compounds. A PEEK-WC membrane was obtained by VIPS/ NIPS technique using a more sustainable solvent (Tamisolve® NxG), with subsequently surface solfanation and doped with Ru. The modified membrane was characterised with different techniques and subsequently tested for the model compounds hydrogenation under mild conditions, achieving 75% furfural conversion and 57.5% furfuryl alcohol selectivity at 85 °C and 18 bar, while only 33% vanillin was converted to vanillin alcohol. The TOF for furfural resulted comparable to that of previously tested catalysts in conventional reactors. The microreactor performed in a stable manner for about 90 h with less than 1% Ru leached out in solution, outperforming previously tested Ru-PES membrane.