To reduce the environmental pollution caused by medical protective materials, such as masks and protective clothing, biodegradable antibacterial materials have received more and more attention in recent years. In this study, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(butylene-adipate-co-terephthalate) (PBAT) were electrospun together and then treated with nano-TiO2to develop and evaluate a biodegradable, antibacterial nanofiber membrane for medical protective fabric. The SEM images displayed that the nanofiber membrane with a mass fraction of 13 and a mass ratio of 50:50 PHBV/PBAT had the smallest diameter and the best morphology of all samples. In addition, the mechanical properties test and water contact angle test results demonstrated that the PBAT/PHBV composite nanofiber membrane had better mechanical properties and hydrophobicity without compromising its fundamental structure than pure PHBV. The addition of TiO2nanoparticles decreased the fiber diameter of this nanofiber membrane. When the TiO2concentration was 1.0 wt%, the average fiber diameter was 367 nm, which might approach the sub-micron level. Meanwhile, the presence of TiO2reduced adhesion between fibers of the PBAT/PHBV membrane, resulting in a more uniform fiber distribution. Additionally, the elongation at the break of the PHBV/PBAT/TiO2nanofiber membrane with 1.0 wt% TiO2was raised from (135 ± 5)% to (203 ± 2)%. The PHBV/PBAT/TiO2nanofiber membrane containing 1.0 wt% TiO2inhibited Escherichia coli and Staphylococcus aureus, and its antibacterial rate was over 98%. In this research, we successfully prepared composite materials that were both biodegradable and antibacterial, which can be applied in the field of medical protection. It can promote the development of protective textile materials in the direction of functionalization and degradation.