Candle soot (CS) nanoparticles exhibit excellent superhydrophobic and superoleophilic properties, making them an ideal absorbent for separating oil and oil/water mixtures. Although their cost‐effectiveness is attractive, the challenges associated with recovering soot nanoparticles after oil absorption and producing secondary pollutants have limited their attention. Our study demonstrates the synthesis of CS nanoparticles embedded polystyrene (PS) nanofibrous membranes with excellent stability, surface‐to‐volume ratios, and flexibility. CS‐incorporated composite membrane with a rough surface showed a water contact angle (WCA) of 156° ± 1.5°, about 20% higher than the smooth pristine PS membrane. The CS‐based composite membrane also demonstrated improved performance as an absorbent, owing to its hydrophobic characteristics linked with surface roughness when employed for separating oil from oil/water mixtures. Furthermore, when exposed to four different oils, the CS‐based membrane displayed a higher absorption capacity (up to ≈120 g oil/g membrane) than the pristine membrane. Using a gravity‐assisted continuous oil/water separation setup, we measured the oil permeate flux using nanofiber mats as a membrane. Compared to the original membrane, the modified membrane showed enhanced oil permeate flux of ~2873 ± 122 L m−2 h−1 and separation efficiency of over 99%. A superhydrophobic polystyrene nanofibrous membrane embedded with candle soot nanoparticles was fabricated using the electrospinning technique. Nanofibrous membranes incorporated with candle soot nanoparticles were used to separate miscible and immiscible oil/water mixtures. The nanoparticle‐incorporated membrane demonstrated higher oil permeate flux than the pristine polystyrene nanofiber‐based membrane. The enhanced oil sorption capacity and permeate flux of the modified membrane were attributed to improved surface roughness and surface functional groups.