Phosphorus-containing flame retardant (HBAEA-DOPO) for epoxy resin was synthesized by addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with bis[2-(4-hydroxybenzylideneamino) ethyl]amine (HBAEA) that was synthesized via 4-hydroxybenzaldehyde with diethylenetriamine. HBAEA-DOPO was mixed with 4,4 0-diaminodiphenyl sulfone to co-cure the epoxy resin of diglycidyl ether bisphenol A. The silane modified nano-silica (nano-SiO 2) was used to reinforce the epoxy resin. Thermal stability and dynamic mechanical properties of the cured epoxy materials were studied with the use of thermogravimetric analysis and dynamic mechanical thermal analysis. Flame retardance and burning behavior were evaluated by the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry. The cured epoxy materials have excellent thermal stability, and the temperatures at the maximum weight loss rate are over 384.0 C. The characteristic temperature corresponding to 5.00 wt% of thermal decomposition reaches 341.5 C as 1.00 wt% of phosphorus content is loaded. Flame retardant grade meets the V-0 level. The fire residue mass gradually increases with HBAEA-DOPO and nano-SiO 2. The characteristics of high flame retardance and smoke suppression of HBAEA-DOPO and nano-SiO 2 on the cured epoxy composites have been demonstrated to be related to char formation and intumescent flame retardance in the condensed phase.