Time-programmed release behaviors of different bioactive substances, enough mechanical properties and good biocompatibility of the scaffold play an important role in vascular tissue regeneration. In this paper, ultrafine fibers with diverse release behaviors were prepared by emulsion or suspension electrospinning from poly(L-lactide-co-glycolide) (PLGA) or poly(ethylene glycol)-b-poly(L-lactide-co-caprolactone) (PELCL), designated as E-PLGA, EH-PLGA, and EH-PELCL, respectively. Chitosan hydrogel was in situ encapsulated in the fibers by suspension electrospinning to provide the carriers for water-soluble bio-additives. To determine the potential applications in vascular tissue engineering areas, morphology and structure of the obtained fibers, the hydrophilicity, mechanical properties, release behaviors, and cytobiocompatibility of the electrospun membranes were investigated. Scanning electron micrographs showed that the diameter of the fibers was in the range of 1501380nm. The hydrogel was encapsulated and distributed discretely into the fibers, which was demonstrated visually by transmission electron micrographs and confocal laser scanning microscopy images. All the membranes exhibited good hydrophilicity and excellent mechanical properties, comparable with human coronary artery. The encapsulation efficiency of a protein model, horseradish peroxidase was up to 70%. Diverse release behaviors were obtained and EH-PELCL showed faster release rate than EH-PLGA and E-PLGA fibers. The fibroblast could adhere, spread, and proliferate on the membranes in good condition showed good cytobiocompatibility of the membranes. This experiment proved that the obtained E-PLGA, EH-PLGA, and EH-PELCL electrospun fibrous scaffolds with enough mechanical properties, different release rates of protein drugs and good cytobiocompatibility could be used as vascular scaffolds for further study.