A series of flame-retardant epoxy resins (EPs) containing either phenethyl-bridged 9 or 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative (bisDOPO) were prepared. The flame-retardant properties of bisDOPO on EP composites were characterized by the limiting oxygen index (LOI), the UL-94 vertical burning, and the cone calorimeter test (CCT).The LOI of the EP/bisDOPO composites increased from 21.8% to 38.0%, and the hybrids with the 10 wt% bisDOPO obtained a V-0 rating in the UL94 vertical burning test. The char residue following the CCT showed intumescent structures with continuous and compact surfaces that can effectively suppress the spread of the flame and extinguish the fire. This was confirmed through both visual observation and scanning electron microscopy (SEM) measurements. The flame-retardant mechanism was studied by Fourier transform infrared spectroscope (FTIR), thermogravimetric analysis/infrared spectrometry, SEM/energy-dispersive X-ray, and pyrolysis-gas chromatography/mass spectrometry. Overall, bisDOPO was an effective flame retardant with potential applications within EP.