Poly (ether ester) elastomer, a segmented copolymer, recently has attracted a wide attention for its unique properties such as elasticity, low temperature impact resistance and chemistry resistance. In this work, a range of poly (ether ester) s were synthesized via a two-step polymerization method using poly (ethylene terephthalate) (PET) as rigid segment and poly (ethylene glycol) (PEG) as flexible segment. The effects of the molecular weight (1000-8000 g/mol) and the weight ratios with PEG (30/100-70/100) of PET segments on the performance of synthetic copolymers were investigated. The chemical structure, thermal properties and hydrophilic performance of the copolymers were respectively characterized. Additionally, the practical block ratios of PEG/PET were calculated by the 1H-NMR Spectra of the copolymer after Soxhlet extraction. Through the obtained results, it revealed that increasing the molecular weight or content of PEG could enhance the hydrophilic performance of the copolymers and reversely reduce its thermal stability. It was shown that the reactivity of PEG in the polymerization process was weakened when its molecular weight was above 4000 or weight ratio with PTA was higher than 60/100, subsequently affected the practical block ratios of PEG/PET in the resulting poly(ether ester)elastomers.