We functionally modify a decellularized porcine aortic valve using a novel complex biologically active cyclic- (c)-RGD modified with branched polyethylene glycol (PEG), namely, c-RDG-PEG. Human umbilical vein endothelial cell (HUVEC) adhesion and proliferation were detected for up to 8 d after seeding on the scaffold. (1)H nuclear magnetic resonance (D2O) showed signal peaks at 7.27 and 7.38 ppm associated with protons of the phenyl group in c-RGD-PEG. Attenuated total reflectance Fourier transform infrared spectroscopy showed characteristic peaks for PEG at 1100 and 1342 cm(-1). These represented vibration peaks of C-O and -CH2 bonds, suggesting successful grafting of c-RGD-PEG to a decellularized porcine aortic valve (DPAV). The tensile strengths were significantly increased in the c-RGD-PEG-DPAV group compared to the native valve and DPAV groups (P < 0.05), while the elastic modulus was sigficantly decreased in the c-RGD-PEG-DPAV group compared to the native valve and DPAV groups (P < 0.05). HUVEC proliferation was significantly higher in the c-RGD-PEG-DPAV group than in the PEG-DPAV and DPAV groups (P < 0.01). Maximum adhesion occurred at 4 h, and on the 8th day, a confluent and compact monolayer formed on the valve surface. The modified DPAV resulted in good adhesion and proliferation of endothelial cells and is an appropriate approach to modify tissue engineered heart valves for promoting endothelialization.