This work is devoted to the creation of biocompatible fibrous materials with a high antimicrobial effect based on poly-3-hydroxybutyrate (PHB) and chlorophyll (Chl). The data obtained show the possibility of obtaining fibrous materials from PHB and Chl by electrospinning methods. The obtained electrospun matrices were investigated by the SEM, DSC and FTIR methods. Various key properties of the matrices were evaluated, including hydrophilicity and mechanical strength, as well as photodynamic and light-dependent antimicrobial effects against the conditionally pathogenic microorganism Staphylococcus aureus. The results demonstrate a significant improvement in electrospinning properties for a concentration of 0.5% Chl and a reduction in fiber formation defects, as well as an increase in the strength of nonwovens. It was found that the antimicrobial potential of Chl-PHB (with concentrations of Chl of 1.25 and 1.5%) is higher than that of Chl in free form. It was also determined that irradiation increases the inhibitory effect of Chl, both in free form and in the form of a complex with a polymer.