Chitosan‐based flame‐retardant CS–Co–DOPA (CCD) was synthesized by the neutralization reaction of 10‐hydroxy‐9,10‐dihydro‐9‐oxo‐10‐phosphaphenanthrene‐10‐oxide (DOPA) with chitosan‐cobalt complex and fully characterized by scanning electron microscopy (SEM), energy‐dispersive spectrometer, x‐ray diffraction, X‐ray photoelectron spectroscopy (XPS), optical emission spectrometer, and Fourier transform infrared (FTIR) characterizations. The epoxy resin (EP) modified with CCD exhibited good flame retardancy. With the addition of 5 wt% CCD, the EP/CCD achieved UL‐94 V‐1 rating and possessed limiting oxygen index (LOI) value of 30%. Cone calorimetry (CC) test demonstrated that EP/CCD resulted in a remarkable reduction of peak smoke production rate (pSPR) and total smoke production (TSP) by 63% and 40%, respectively, showing an outstanding smoke suppression. The char residue obtained from the CC test was further characterized using SEM, FTIR, Raman, and XPS techniques. The results revealed that CCD facilitated the formation of a dense and compact char layer on EP during combustion, thereby impeding gas and heat transfer. In addition, TG‐IR was employed to investigate the gas‐phase flame‐retardant effect of EP/CCD composites, which revealed that CCD promotes the release of water, CO2, and other incombustible gases, altering the decomposition path of EP.