In this work, a novel organic–inorganic hybrid catalyst ([Mo6O18] @GO-NH2) was synthesized by covalent attachment of Lindqvist type polyoxometalate [(C4H9)4N]2[Mo6O19] on the surface of graphene oxide (GO). To provide the hybrid catalyst, graphene oxide was covalently modified with an aminosilane, followed by treatment with a polyoxometalate complex. The resulting catalyst was identified by different analytical techniques TG, SEM, XRD, BET, EDX, FT-IR, and N2 adsorption–desorption. [Mo6O18] @GO-NH2 was used as an efficient catalyst for the preparation of various benzimidazoles. The result showed high activity, recoverability, reusability, and durability of the designed catalyst under applied conditions.