Polymeric small-diameter vascular grafts (SDVGs, inner diameter, < 6 mm) with characteristics, such as thrombo-protection and adequate short-term as well as long-term patency are still in the development and exploration stage. In this study, based on the gas signaling molecule release strategy, SDVGs were prepared by electrospinning using poly(L-lactide-co-ɛ-caprolactone) (PLCL) and gelatin (Gel). Bivalirudin (BVLD) and epigallocatechin gallate-copper (EGCG-Cu) complex were loaded into SDVGs to improve hemocompatibility and nitric oxide (NO) release, respectively. Vascular grafts manifested drug release for up to 40 days in vitro; BVLD effectively inhibited thrombosis while the EGCG-Cu complex catalyzed the NO production from endogenous donors (S-nitroso glutathione (GSNO) and glutathione (GSH)), thereby conferring vascular grafts with functions similar to that of the natural vascular endothelium layer. Both in vitro and in vivo tests demonstrated that SDVGs co-loaded with BVLD and EGCG-Cu (PG-EB) could effectively inhibit thrombosis, alleviate inflammation, and suppress the proliferation of smooth muscle cells (SMCs) while promoting the proliferation of endothelial cells (ECs), and finally regenerate vascular tissues. In vivo animal experiments demonstrated that vascular grafts could promote endothelialization and vascular remodeling. In summary, our simultaneous utilization of BVLD and EGCG-Cu may offer a promising avenue for the fabrication of in situ regenerable SDVGs.