An extracellular matrix-like poly (ε-caprolactone) (PCL)/gelatin core-shell nanofibrous scaffold with high hydrophilicity was developed by coaxial-elecrospinning. However, the behavior of vascular endothelial cells (ECs) on the modified scaffold remains limited. In this study, human umbilical vein ECs (HUVECs) were seeded onto PCL scaffolds with or without gelatin. Morphological changes of HUVECs were observed under confocal laser scanning microscopy (LSCM). HUVECs’ adhesion, proliferation and apoptosis were detected by MTT assay and flow cytometry (FCM). Our results showed that HUVECs on PCL/gelatin scaffolds with identical polygonal and cobblestone-like characteristics reached confluence after 7 days. Modification of PCL nanofibers significantly promoted the attachment of HUVECs onto scaffolds within 1 hour. Compared to pristine PCL, a two-fold increase in proliferation of HUVECs was also observed after 7 days, whereas the apoptosis of HUVECs was obviously reduced by 40% on the modified scaffolds. In summary, these results indicated modified PCL/gelatin scaffold developed by coaxial-elecrospinning can increase the adhesion, proliferation, and suppress apoptosis of HUVECs, suggesting it has a great potential and promising vascular graft in tissue engineering applications.