CNT/epoxy composite film (CECF) was prepared and used to fabricate the interlayer stiffened and reinforced photothermal synergistic curing glass fiber-reinforced polymer (GFRP) composites, and the influence of the photothermal effects of CECF on compressive strength and failure mechanism of the composite was investigated. Compared to GFRP composite, the uniform and wide temperature distribution in the in-plane and thickness direction was exhibited due to the heat from the lattice vibrations induced by photothermal conversions of CECF, thereby facilitating the decomposition of the thermal initiator and the increase of the curing degree in the CECF/GFRP composite. The in-plane shear modulus and interlaminar shear strength (ILSS) of the CECF/GFRP composite were 12.2% and 13.7% higher than those of the GFRP composite, respectively, indicating the enhanced deformation resistance and interfacial adhesion of the interlayer region. The compressive strength of the CECF/GFRP composite was increased by 14.1% relative to the GFRP composite, which was ascribed to restricted kink-band and delayed delamination damage during the compression process of composite.