Metal phthalocyanine (MPc) has a great saturation response value, but its low conductivity and slow response speed limit its practical application. A novel hybrid material composed of graphene quantum dots (GQDs) and metal phthalocyanine derivatives has been obtained. GQDs can be anchored onto the surface of MPc nanofibers through π–π stacking. The response to NO2 can be significantly enhanced under certain component proportion matching, which is much better than their respective response to NO2. The introduction of GQDs greatly increases the conductivity of phthalocyanine fibers, leading to a faster response of the hybrid material. In addition, the reproducibility, selectivity and stability of the hybrid materials are excellent, and the minimum response concentration can reach 50 ppb. Ultra-low-power laser irradiation was used to solve the problem of slow recovery of metal phthalocyanine. Overall, we present the advantages of combining MPc nanofibers with GQDs and pave a new avenue for the application of MPc–GQD hybrids in the gas sensing field.