Nitrogen (N-GQD) as well as nitrogen and phosphorous co-doped (NP-GQD) graphene quantum dots were demonstrated as novel, low cost, green and highly effective flame retardants and smoke suppressants for polyacrylonitrile (PAN) nanocomposites. The N-GQD and NP-GQD samples were synthesized by hydrothermal method with citric acid as the main reactant. For the first time, the flame retardant and smoke suppressant properties of the NP-GQD were studied. The GQDs were introduced into PAN by solvent blending route. Subsequently, thermal stability, flame retardancy, fire behavior, fire hazard and structure of the residual char were investigated by thermogravimetric analysis (TGA), UL-94 vertical burning test, cone calorimetry, FE-SEM, and Raman spectroscopy. Results showed that both PAN/N-GQD and PAN/NP-GQD nanocomposites had higher flame retardancy and smoke suppressant behavior in addition to lower fire hazard properties than neat PAN. Furthermore, the residual chars for the nanocomposite samples were increased in comparison to the neat PAN. The improvements were even more significant in case of the PAN/NP-GQD due to the synergistic effect of nitrogen and phosphorous. The improvements were mainly ascribed to the ability of the N-GQD and NP-GQD to provide stronger and larger protective char barrier layers, which was even more pronounced in case of the NP-GQD.