Graphene-wrapped ZnO nanocomposites were fabricated by a simple solvothermal technology with a one-pot route. The structure and morphology of these as-fabricated samples were systematically characterized. The adding of graphene enhanced the content of the oxygen vacancy defect of the sample. All gas-sensing performances of sensors based on as-prepared samples were thoroughly studied. Sensors displayed an ultrahigh response and exceptional selectivity at room temperature under blue light irradiation. This excellent and enhanced toluene gas-sensing property was principally attributed to the synergistic impacts of the oxygen vacancy defect and the wrapped graphene in the composite sensor. The photo-activated graphene-wrapped ZnO sensor illustrated potential application in the practical detection of low concentrations of toluene under explosive environments.