Present study reports polycarbonate (PC) nanofibers functionalized with industrial grade activated charcoal for emphatic oil-water separation and recovery of petroleum oils and organic solvents from oily wastewater. The developed PC nanofibers demonstrate hydrophobicity (water contact angle of 133°) and oleophilicity (oil and/-or solvent contact angle is equal to 0°), simultaneously. The functionalized PC nanofibers exhibit average permeation flux of 10,834.5 L m −2 h −1 and 39,886.5 L m −2 h −1 toward diesel, and n-Hexane solvent, respectively. Developed PC nanofibers demonstrated an excellent oil recovery toward petroleum oil products like petrol, diesel, and engine oil, which was found to be 308%, 872%, and 1738%, respectively, till 10 washing cycles. Thermogravimetric analysis of developed PC nanofibers revealed thermal stability up to 350 °C, thereby demonstrating its applicability in harsh environmental conditions. Functionalization of PC polymer nanofibers with activated charcoal was confirmed using FTIR study. The morphological analysis of charcoal functionalized PC nanofibers revealed a heterogeneous rough patterned textures with a porosity (which facilitate the air-pockets for improved hydrophobicity) manifesting inside the fibers. The pH-based performance (pH range of 2-14) demonstrated that the developed microfibers maintain its hydrophobicity ad service durability under harsh acidic and alkaline mediums (corrosive environments). The PC nanofibers demonstrate simultaneous hydrophobic-oleophilic behavior which is well explained using principal Cassie-Baxter's theory. The successive results demonstrate that the activated charcoal functionalized PC microfibers could be successfully utilized for practical recovery of oil/organic solvents from oily wastewater, and for the oil-spill cleanups.