Furfural is regarded as an important platform chemical with a wide range of applications. Because of the low concentration of furfural in the hydrolysate, energy-saving and environmentally friendly separation method is urgently demanded. In this work, a homogeneous mixed matrix membrane (MMM) consisting of Zn2(bim)4 as inorganic filler and PMPS (polymethylphenylsiloxane) as polymer matrix was successfully fabricated by employing a solution-blending method. The vapor permeation experiments demonstrated that the pervaporation separation index (PSI) increased with increasing temperature, indicating the high performance of the as-synthesized Zn2(bim)4-PMPS membrane for separating furfural at high temperature. Hereafter, the dehydration reaction of xylose into furfural in a membrane reactor coupled with Zn2(bim)4-PMPS membrane was carried out. In contrast to the conventional reactor, the furfural yield in membrane reactor kept increasing due to the in-situ recovery of furfural by vapor permeation. The highest furfural yield achieved till now was 41.1% at 140 °C in aqueous solution. Owing to the intrinsic separation properties of Zn2(bim)4 crystals and the effective enhancement of membrane stability by interaction of Zn2(bim)4 with PMPS matrix, the Zn2(bim)4-PMPS membrane coupled reactor exhibited better performance than pure PMPS membrane coupled reactor.