The macroscopic mechanical properties of fiber reinforced concrete are closely related to the interfacial bonding of fiber/matrix. In this paperthe effect of graphene oxide (GO) on the interfacial bonding of polyvinyl alcohol fiber (PVA)/matrix was studied by molecular dynamics simulation. The results show that when GO and PVA fiber are connected by covalent bondthe tensile force required for PVA fiber to be pulled out from concrete is the largestand the presence of GO can improve the interfacial bonding performance between fiber and matrix. The concrete matrix and GO are mainly connected by calcium-oxygen bonds and hydrogen bondsin which the number of calcium-oxygen bonds is large and the strength of chemical bonds is high. Howeverwhen GO and PVA fiber are physically connectedGO and PVA fiber are only connected by weak hydrogen bondswhich has a negative effect on the bonding performance of interface. In additionGO is bound by more ionic bonds and hydrogen bondsthe atomic translational motion is reducedand the interfacial bonding performance with matrix is improved.