The rising peril of oil spills, contretemps of oil carriers, and oil seepages polluting our inestimable water bodies and blemishing marine lives are perilous and grievous matters of concern. Silk is one of the utmost appreciated materials for wastewater treatment in arrears to its superhydrophobicity while finding the legitimate solution to the oil spilling problem by offering a safe operating space, considering several such losses due to oil spills. The present study collates oil–water segregation capacities of raw silk, degummed silk, and degummed silk modified with electrospun polylactic acid (DG-Silk/PLA). The oil–water separation capacities of reported samples were assessed by performing a w/w oil absorption capacity test, oil–water separation test, and permeation flux study for petrol, diesel, and engine oil. DG-Silk/PLA showed the maximum oil absorption capacity (petrol ~ 1224%, diesel ~ 1478%, and engine oil ~ 2049%), attributed to its superhydrophobicity (WCA ~ 165 ± 2°) and superoleophilicity (OCA ~ 0°). The optimum oil–water separation was obtained in DG-silk/PLA (76.67–82.57%), followed by the degummed silk and raw silk (RS), respectively. DG-Silk/PLA exhibited enhanced permeation flux for oils than RS and biodegradability than DG-silk. The successive results illustrated that the DG-Silk/PLA could be successfully employed for applied oil–water separation or oil spills cleanup due to their exceptional characteristics.