Two novel polyesterurethane materials, PEU1 and PEU2, were synthesized via nontoxic and isocyanate-free route by simple conversion of two epoxides 1,2-epoxy-3-phenoxy propane (2) and styrene epoxide (3) utilizing CO2. Epoxides 2 and 3 were converted to the respective cyclic carbonates 4 and 5 by a new set of cobalt-based catalyst 1a in the presence of 10 bar of CO2 and 80 °C temperature without using cocatalyst tetrabutylammonium bromide (TBAB). The mechanistic pathway of the catalysis reaction for the cycloaddition of epoxides with CO2 to generate the cyclic carbonates was investigated by several spectroscopic techniques and utilizing analogous zinc-based 1D coordination polymer 1b, which does not act as an efficient catalyst in the absence of TBAB. Cyclic carbonates 4 and 5 were converted to the respective polyesterurethanes PEU1 and PEU2 sequentially by first synthesizing the ring-opened diols 6 and 7 reacting with ethylenediamine and subsequently annealing the respective diols 6 and 7 at 120 °C in the presence of terepthalyl chloride and triethylamine. The polyesterurethanes PEU1 and PEU2 were characterized by multinuclear NMR and FTIR. PEU1 was also characterized by MALDI-TOF mass spectrometry. The thermal studies of PEU1 and PEU2 showed the stability up to 200-270 °C. The number-average and weight-average molecular weights were determined for PEU1 and PEU2 by GPC analysis. The weight-average molecular weight for PEU1 was found to be 5948 with a polydispersity of 1.1, and PEU2 showed the weight-average molecular weight as 4224 with a polydispersity of 1.06.