Several types of nanostructured hybrid fibrous materials containing poly(3-hydroxybutyrate), nanoparticles from iron oxide (Fe3O4) and titanium dioxide (TiO2), and chitosan or chitosan oligosaccharides (COS) were prepared. The design of the surface of the materials and their magnetic properties were tailored purposefully by conjunction of electrospinning and electrospraying. The surface and bulk morphologies of the obtained nanostructured materials were examined by SEM. Further, the distribution of Fe3O4 and TiO2 nanoparticles was estimated by TEM analyses, as well as their surface chemical composition was determined by XPS. It was found that the simultaneous electrospinning and electrospraying of Fe3O4/chitosan or TiO2/COS dispersions resulted in uniform distribution of the nanoparticles along the length of the fibers, while electrospraying of the mixed Fe3O4/TiO2/chitosan dispersion led to agglomerate formation. Furthermore, the nanostructured hybrid materials preserved the magnetic properties of Fe3O4 embedded therein. It was demonstrated that the hybrid materials of different designs displayed excellent photocatalytic activity under UV light irradiation against a model organic contaminant-methylene blue, even after threefold use of the materials.