Side-chain crystallizable comb-like polymers can be used as polymeric thermal energy-storage materials. Diethylene glycol hexadecyl ether acrylate (C16E2AA) was synthesized with sodium alkoxide using diethylene glycol hexadecyl ether (C16E2) and acryloyl chloride as reactants. C16E2AA was prepared by free radical polymerization to form a comb-like polymeric phase change material, poly(diethylene glycol hexadecyl ether acrylate) (PC16E2AA). A series of sheath/core composite submicron fibers were coaxially electrospun using PC16E2AA as the core and poly(acrylonitrile-co-vinylidene chloride) as the sheath. Results indicate that C16E2AA and PC16E2AA were synthesized in high yield. The average molecular weight and polydispersity index of PC16E2AA were 29,800g/mol and 3.17, respectively. PC16E2AA melted at 33.8? and crystallized at 25.8?. The melting and crystallization enthalpy for PC16E2AA were 90 and 85J/g, respectively. PC16E2AA was thermally stable below 326?. Coaxial submicron fibers with smooth surface and average diameter ranging from 341 to 371nm were electrospun. The optimum feed rate of the sheath and core components for fabricating thermo-regulated submicron fibers with high enthalpies were 0.125 and 0.375mL/h, respectively. The fibers can absorb 50J/g at approximately 37? and release 48J/g of heat at approximately 32?.