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AbstractPolycaprolactone (PCL) is one of the most usable polymers in biomedical applications. Despite this, PCL has a natural hydrophobic character and a lack of active site for interaction with other materials. For overcome this limitation, surface modification using polyethyleneimine (PEI) was carried out to provide suitable hydrophilic surface for cell adhesion and proliferation. The 3D printed scaffolds were analyzed by scanning electron microscopy (SEM), attenuated total reflection?Fourier transform?infrared (ATR?FTIR) spectroscopy, contact angle, and ninhydrin assay. Finally, enzymatic degradation behavior and cellular activities were carried out to investigate the possible application in bone tissue engineering. The results indicated the formation of uniform PEI coating along with increase in the surface hydrophilicity through absorption of 43% of free amine groups, improvement of enzymatic degradation of PCL scaffolds about four times from 1.51% to 5.77% after 4?days. Also, the biological studies indicated that modification of PCL scaffolds surface with PEI provided a suitable platform for attachment, differentiation and proliferation of MC3T3 cells in the PCL?based scaffolds. Taken together, the results suggest that the 3D composite scaffolds could be used in bone tissue engineering.