Biodegradable polylactic acid (PLA) was used to fabricate nonwoven fabrics via the melt blowing process, followed by electrospinning to deposit a nanofiber membrane. This composite process yielded PLA melt-blown/electrospun composite materials with excellent filtration performance. The effects of the solution concentration and spinning duration on the composite structure and material performance were investigated. The optimal composite was produced using a 10 wt.% PLA spinning solution prepared with a solvent mixture of dichloromethane (DCM) and N, N-dimethylformamide (DMF) in a 75/25 weight ratio. The process parameters included a spinning duration of 5 h, 18 kV voltage, 1.5 mL/h flow rate, and 12 cm collection distance. The resulting composite achieved a filtration efficiency of 98.7%, a pressure drop of 142 Pa, an average pore size of 5 μm, and a contact angle of 138.7°. These results provided optimal process parameters for preparing PLA melt-blown/electrospun composite filtration materials. This study highlights the potential of hydrophobic PLA composites with high filtration efficiency and low air resistance as environmentally friendly alternatives to traditional non-degradable filtration materials.