As ideal tissue engineering scaffold, surface feature plays an important role in cell adhesion and proliferation. In order to improve cytocompatibility of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and polyethylene oxide (PEO) synthetic materials, in this study, photochemical surface modification is applied in electrospinning field for the first time. Azidobenzoic acid-modified gelatin (AZ-gelatin) as bioactive protein is successfully fixed on PHBV/PEO electrospun mats by photochemical technique without any crosslinking agent. In vitro degradation and cell culture results show that PHBV/PEO/AZ-gelatin electrospun mats have excellent cell adhesion and proliferation compared with PHBV and PHBV/PEO electrospun mats. But, by contrast with PHBV/PEO electrospun mats, the fiber diameter of PHBV/PEO/AZ-gelatin mats increased, and the porosity and mechanical properties decrease. Nonetheless, PHBV/PEO/AZ-gelatin-0.01 mg mL(-1) electrospun mats have shown better morphology (fiber diameter 600 nm, porosity 88%), mechanical properties (4.2 MPa), and water vapor transmission rate (2301 g m(-2)day(-1)), which has great potential as artificial skin scaffold in tissue regeneration field.