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A novel pH and temperature sensitive penta-block (PAE-PCL-PEG-PCL-PAE (poly (β-amino ester))) was synthesized followed by preparing poly (ethylene glycol)(PEG)-Poly (ε-caprolactone (CL)) (PCL-PEG-PCL) triblock copolymer by ring-opening polymerization.Their physicochemical properties of triblock and penta-block copolymers were characterized by 1H-NMR spectroscopy and gel permeation spectroscopy.This poly (β-amino ester) (PAE) based hydrogels showed an injectable,degradable and pH/temperature sensitive hydrogel.Aqueous media of the penta-block copolymer changed from a sol phase to a gel phase with increasing both of temperature and pH.