Graphene oxide (GO), as a two-dimensional structure material, has attracted widespread attention in the field of molecule sieving. However, GO-based membranes usually exhibit undesirable separation performance because the microstructure of GO is difficult to adjust. Herein, a novel double-crosslinking strategy for tuning the interlayer spacing of GO is reported. The hybrid membrane fabricated by the double-crosslinking strategy was used for pervaporation (PV) dehydration of isopropanol. To achieve high-performance of the PV hybrid membranes, the effects of operating cycles, chitosan concentration, and GO concentration were systematically investigated. The PV hybrid membranes were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, water contact angle measurement, and scanning electron microscopy. The results demonstrate that the interlayer of GO can be adjusted successfully by the double-crosslinking strategy. The fabricated hybrid membrane containing 0.1 wt % GO exhibited excellent performance with a flux of 4391 g/m2h and a separation factor of 1491, which indicated that the double-crosslinking strategy may extend the applications of GO in the field of membrane separation.