Biobutanol is an attractive renewable biofuel mainly obtained by the acetone-butanol-ethanol (ABE) fermentation process. Nevertheless, the alcohol concentration has to be limited to a maximum of 2 wt % in ABE fermentation broths to avoid butanol toxicity to the microorganisms. The pervaporation (PV) membrane process is a key sustainable technology for butanol recovery in these challenging conditions. In this work, the grafting of azido-polydimethylsiloxane (PDMS-N3) onto a PDMS-based multiblock copolymer containing alkyne side groups led to a series of original membrane materials with increasing PDMS contents from 50 to 71 wt %. Their membrane properties were assessed for butanol recovery by pervaporation from a model aqueous solution containing 2 wt % of n-butanol at 50 °C. The membrane flux J50μm for a reference thickness of 50 μm strongly increased from 84 to 192 g/h m(2) with increasing PDMS content for free-standing dense membranes with thicknesses in the range of 38-95 μm. At the same time, the intrinsic butanol permeability increased from 1.47 to 4.68 kg μm/h m(2) kPa and the permeate butanol content was also strongly improved from 38 to 53 wt %, corresponding to high and very high membrane separation factors of 30 and 55, respectively. Therefore, the new grafted copolymer materials strongly overcame the common permeability/selectivity trade-off for butanol recovery by a sustainable membrane process.