Artificial vascular grafts play an important role in the clinical treatment of cardiovascular diseases due to the lack of autografts. Artificial vascular grafts, especially for small-diameter artificial vascular grafts, usually encounter the problems such as in-stent restenosis, thus limiting their application in clinical treatment. Endothelialization of artificial vascular grafts can improve their hemocompatibility and maintain their long-term patency. It has been confirmed that multifunctional gene delivery systems can promote the proliferation of vascular endothelial cells(ECs) and help achieve the rapid endothelialization of artificial vascular grafts. Recently, functional peptides and cationic polymers have provided an effective approach for the development of low-toxic and highly efficient multifunctional gene delivery systems. In this review, functional peptides, target genes and polycationic gene carriers used in the transfection of vascular ECs are detailedly introduced. Based on polycationic gene carriers, the current development of multifunctional step-by-step targeting gene delivery systems for promoting the proliferation of ECs and endothelialization are highlighted. Finally, some perspectives on achieving rapid endothelialization via gene transfection are also presented.