In this article, inherent flame-retardant epoxy ether, 9,10-dihydro-9-oxa-10-[1,1-bis(4-glycidyloxyphenyl)ethyl]-10-phosphaphenanthrene 10-oxide (DPBAEP), with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide moieties was synthesized via an economical method and was used to improve the flame retardancy of 4,4′-tetradiglycidyl diaminodiphenyl methane (TGDDM). A series of epoxy resins were prepared and cured with 4,4′-diaminodiphenyl sulfone. The glass transition temperatures (Tg) of resin composites were above 243°C and decreased only slightly after DPBAEP was added. The thermal stabilities under the nitrogen (N2) and air atmosphere were also measured using thermogravimetric analysis. The results indicated that DPBAEP had a high decomposition temperature and affected the thermal degradation and promoted the charring of resins. When only over 5 wt% of DPBAEP was introduced, the thermosets obtained a high limiting oxygen index value of around 33.0%, achieved vertical burning V-0 rating and presented fast-swelling char barriers. In order to better understand the flame-retardant mechanisms, the residual char was investigated by scanning electron microscopy observation and Fourier transform infrared spectra. We inferred that the phosphorus (P) moieties reacted with the resin matrix, which played a significant role in promoting the formation of char with special structure, as well as making it rich and tough enough. This kind of char barrier could protect the underlying resin matrix against oxygen and heat transfer and inhibited volatile combustible from diffusing to the flame. Hence, thanks to the synergistic effect of P–N and the excellent compatibility, DPBAEP could impart excellent flame retardancy to TGDDM epoxy resin.