The objective of this work was to prepare hydrogel films, as semi-interpenetrating polymer networks (semi-IPN), based on polyethylene glycol-co-fumarate (PEGF) and chitosan (Ch) blends. Hydrogel films were prepared by free radical cross-linking of PEGF, an unsaturated aliphatic polyester, in the presence of N-vinyl pyrrolidone (NVP), camphorquinone (CQ), and N,N-dimethylp-toluidine (DMPT) as a cross-linking, photoinitiating, and accelerating agent, respectively. The effect of NVP concentration on physicochemical and biological properties of semi-IPN film properties was evaluated. The sol fraction, water vapor transmission rate, and swelling degree of the hydrogel films were also investigated. Antibacterial activity against S. aureus was observed for the photocured blend hydrogels of Ch/PEGF with no toxicity to L929 cells according to the cell viability assays. Blend hydrogel films showing 600 ± 88% of equilibrium swelling degree in water and the lowest sol fraction (3.14 ± 1.22%) were obtained at 20 wt% of NVP content whilst preserving their own cytocompatibility and antibacterial activity. Therefore, this formulation was considered as an optimal semi-IPN blend hydrogel film composition with potential application for wound dressing.