Carboxyl graphene (CG) with two functions of hybridization and crosslinking was incorporated into poly(vinyl alcohol) (PVA) matrix to form PVA/CG mixed-matrix membranes (MMMs). The membranes demonstrated excellent mechanical properties and thermal stability. The improved hydrophilicity and formed crosslinking structure led to moderate swelling. The membrane crystallinity decreased and the free volume was promoted with increasing CG loading amount. The pervaporation (PV) separation performance for ethanol dehydration indicated that both permeation flux and separation factor were enhanced simultaneously at the optimum CG loading. Subsequently, the permeation flux continued to increase while the separation factor declined at higher CG loadings.