In this study DMT(Dimethylterephthalate), NDC(Dimethyl-2, 6-Naphthalene Dicarboxylate) were used to synthesize polyester polyol which shows enhanced storage stability, improved flame retardancy, and good compressive strength. If DMT and NDC react respectively with DEG(Diethylene Glycol) which is kind of linear diol, the obtained polyester polyols tend to crystallize easily after the reaction. In case of DMT, PA(Phthalic Anhydride) which has asymmetric structure was introduced to retard the crystallization. In case of NDC, DPG(Dipropylene Glycol) which has an methyl side chain was introduced to prevent the crystallization. It was found that to introduce DPG was much more effective method to prevent the crystallization than PA. NDC and DMT were reacted together with DPG for various compositions of NDC:DMT(8:2, 6:4, 4:6 mol ratio). The obtained NDC-DMT-DPG based polyester polyol showed improved flame retardancy, and good compressive strength with increasing the content of NDC.