Herein, a novel ceramic tubular supported graphene-polydimethylsiloxane nanocomposite (CT/Gr-PDMS) membranes were fabricated via dip-coating method with various graphene contents (0–0.5 wt%) using tetraethylorthosilicate as the crosslinking agent. The characterizations of graphene-polydimethylsiloxane nanocomposite (Gr-PDMS) were analyzed by Fourier-transform infrared spectroscopy, X-ray diffraction spectroscopy, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. The CT/Gr-PDMS membranes were used to separate the furfural-water mixture via pervaporation (PV) technology. The effects of operating conditions, such as feed concentration, feed temperature, and operation time on the PV performance of CT/0.2Gr-PDMS membrane, which were investigated via a one-factor-at-a-time approach. The PV performance of CT/0.2Gr-PDMS membrane revealed permeate flux (J) of 0.63 kg/m2h, separation factor (α) of 85.65, and PV separation index (PSI) of 53.7 kg/m2h in the appropriate operating condition as feed concentration of 2 wt% at 50 °C for 5 h. Moreover, this work has shown the promising potential of the CT/0.2Gr-PDMS membrane in providing PV technology with a high furfural separation performance.