This study investigates the reutilization of polylactic acid (PLA) waste generated by 3D printing through its transformation into electrospun membranes with tunable morphological, surface, thermal, and filtration properties. Polymer solutions containing 5–10 wt % recycled PLA were prepared in a dichloromethane/dimethylformamide system and characterized in terms of viscosity and electrical conductivity. Increasing PLA concentration raised solution viscosity (41.87–339.83 mPa·s) and reduced conductivity (7.63–1.63 µS·cm⁻¹), promoting the formation of bead-free fibers with larger diameters (0.221–1.213 µm) and enhanced hydrophobicity (contact angles 112.34–124.38°). FTIR confirmed preservation of the polymer chemical structure after recycling and electrospinning, while DSC revealed reduced crystallinity in the fibrous membranes. Exploratory correlation analysis indicated consistent associations between solution properties, fiber morphology, and wettability. Increasing the number of electrospun layers (1–3) generated denser networks with reduced pore size and improved particle retention. Filtration tests conducted under controlled airflow conditions (85 L min⁻¹, 1 cm s⁻¹ frontal velocity, 50 cm² effective area) showed removal efficiencies above 90% for PM2.5 and PM5, while PM1 capture improved with increasing membrane thickness. Quality factor analysis highlighted the trade-off between filtration efficiency and pressure drop, identifying intermediate multilayer configurations as providing a favorable balance. These findings demonstrate that electrospinning offers an effective strategy for converting recycled PLA into structurally tunable membranes with adjustable filtration performance, supporting sustainable valorization of additive manufacturing waste.