Abstract Nanopores generated from the gap among electrospun nanofibers can provide vascular tissues with oxygen, nutrients, and growth factors. Here, we report the first fabrication of poly( l-lactide- co-caprolactone- co-glycolide) (PLCG) electrospun nanofibers. A water-soluble amphiphilic copolymer bearing phosphorylcholine groups (PMB30W) and an antiproliferative (rapamycin) were incorporated into PLCG by solvent blending and subsequent electrospinning. The nanostructure of the electrospun PLCG/PMB30W/rapamycin blended fibers was stable during incubation in phosphate-buffered saline without addition of chemical crosslinkers. Amphiphilic characteristics of PMB30W and hydrophobic nature of rapamycin could make the electrospun PLCG/PMB30W/rapamycin blended fibers stable under a physiologic condition. The electrospun PLCG/PMB30W/rapamycin blended fibers may be preferable for vascular prostheses and tissue-engineered vascular grafts.