Poly(L-lactide-co-caprolactone)/collagen/chitosan (P(LLA-CL)/COL/CS) composite grafts were electrospun in this study. Based on the testing results of mechanical properties, biodegradability and in vitro cellular compatibility, the optimal weight ratio of P(LLA-CL) to COL/CS was set as 3:1. In vivo study was further performed in a canine femoral artery model. The results showed that the 3:1 grafts possessed excellent structural integrity, higher patency rate, better endothelial cells (ECs) and smooth muscle cells (SMCs) growth, as well as higher gene and protein expression levels of angiogenesis-related cues than those of grafts based on P(LLA-CL). The findings confirmed that the addition of natural materials such as collagen and chitosan could effectively improve endothelialization, SMCs incursion in the tunica media, and vascular remodeling for tissue engineering.