Two-dimensional Co ultrathin metal–organic framework nanosheets (Co-UMOFNs) were synthesized and blended into poly (ether block amide) (PEBA) to prepare composite mixed matrix membranes on PVDF supports for the pervaporation of phenol aqueous solution. The membranes were characterized by XRD, ATR-IR, TGA, CA and SEM measurements. Effects of the Co-UMOFNs loading, feed temperature and feed concentration on phenol separation performance were investigated. The results showed that Co-UMOFNs have a two-dimensional layered morphology and have good compatibility with the PEBA. A “brick and mortar” architecture morphology was achieved after incorporating Co-UMOFNs into the PEBA membrane. The amorphous PE segments in the PEBA were turned into a crystalline structure, restricting the motion of PE segments. The filling of Co-UMOFNs slightly improved the thermal stability and hydrophobicity as well. With the increase of the Co-UMOFNs loading from 0% to 40%, the phenol separation factor increased from 27 to 45, and the total flux decreased from 1.2 kg m-2h-1 to 0.42 kg m-2h-1, when separation of 1000 ppm phenol solution at 70 °C. The interlayer galleries induced by the Co-UMOFNs stacking increased the tortuosity, and the crystalline structure of the Co-UMOFNs-PEBA improved the energy barriers of water penetration. Therefore the water flux was inhibited and the phenol separation factor increased. Depression of water permeation can be another protocol to prepare high-performance organophilic pervaporation membranes.