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9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives have been widely used as effective flame retardants. In this study, 6-((bis(2-hydroxyethyl) amino) methyl)-6H-dibe-nzo[c,e][1,2]oxaphosphinine-6-oxide (DHDOPO) was synthesized from DOPO, paraformaldehyde, and diethanolamine, and subsequently used as a reactant for synthesis of flame retarded alkyd resin (FR-ALK). Thermogravimetric analysis (TGA) showed that DHDOPO had relatively high thermal stability and would not decompose at synthesis temperature of ALK. The thermal stability and flame retardancy of ALKs were improved by introduction of DHDOPO. As the mass fraction of phosphorus in FR-ALK increased the decomposition temperature, the char yield in TGA experiments, the fire residue, and time to ignition in cone calorimeter tests increased, and peak heat release rate (PHRR) and total heat release (THR) decreased. Compared with the non-flame retarded ALK the PHRR and THR values of FR-ALK containing 2.5 wt % phosphorus decreased, respectively, by 43.1% and 58.5%.