In order to prepare multifunctional fibrous membranes with hydrophobicity, antibacterial properties and UV resistance, we used silica and titanium dioxide for preparing SiO₂@TiO₂ nanoparticles (SiO₂@TiO₂ NPs) to create roughness on the fibrous membranes surfaces. The introduction of TiO₂ was used for improving UV resistance. N-Halamine precursor and silane precursor were introduced to modify SiO₂@TiO₂ NPs to synthesize SiO₂@TiO₂-based core@shell composite nanoparticles. The hydrophobic antibacterial fibrous membranes were prepared by a dip-pad process of electrospun biodegradable polyhydroxybutyrate/poly-ε-caprolactone (PHB/PCL) with the synthesized SiO₂@TiO₂-based core@shell composite nanoparticles. TEM, SEM and FT-IR were used to characterize the synthesized SiO₂@TiO₂-based core@shell composite nanoparticles and the hydrophobic antibacterial fibrous membranes. The fibrous membranes not only showed excellent hydrophobicity with an average water contact angle of 144° ± 1°, but also appreciable air permeability. The chlorinated fibrous membranes could inactivate all S. aureus and E. coli O157:H7 after 5 min and 60 min of contact, respectively. In addition, the chlorinated fibrous membranes exhibited outstanding cell compatibility with 102.1% of cell viability. Therefore, the prepared hydrophobic antibacterial degradable fibrous membranes may have great potential application for packaging materials.