The focus of the present study is on the fabrication of effective and eco-friendly hybrid electrospun materials based on poly(L-lactide-co-D,L-lactide) (PLDLLA), Fe3O4 and ZnO with an appropriate design for antioxidant and photocatalytic performance. The design of the fibrous materials was purposely tailored in one step by electrospinning and simultaneous electrospinning/electrospraying. Electrospinning of PLDLLA and its mixture with Fe3O4 resulted in the fabrication of materials with design type "in". Furthermore, the surface of the electrospun PLDLLA and Fe3O4-in-PLDLLA was decorated with ZnO particles by simultaneous electrospraying, thus materials with design type "on" were obtained. In this case, quaternized N,N,N-trimethyl chitosan iodide (QCOS) was used as a sticking agent of ZnO particles onto the fiber's surface. Different structures and morphologies of the electrospun materials were observed by SEM equipped with EDX and TEM. TGA and XRD analyses show that the presence of inorganic particles had an impact on the thermal properties and crystallinity of the electrospun materials. Furthermore, the material type "on" showed improved wettability with a water contact angle less than 90° compared to the material type "in" with an angle larger than 90°. In particular, the presence of Fe3O4 imparts complementary magnetic properties, while ZnO considerably increased the antioxidant activity of the fibrous materials. Materials with design type "on" displayed over 70% radical scavenging capacity in contrast to the material type "in" with less than 20% capacity within 30 min of contact. Moreover, the purposely tailored design type "on" materials provided excellent photocatalytic degradation of model organic pollutant methylene blue dye under UV light irradiation even after 5-fold use, and at the end of the fifth cycle these materials degraded more than 90% of the dye. These results reveal not only a strategy for the fabrication of electrospun hybrid bio-based materials with targeted design but also provide a promising, simple and effective way for mitigating water pollution.