Oil separation is crucial for avoiding environmental pollution originating from industrial wastewater and oil spillage; therefore, it is essential to develop techniques for oil separation. Herein, a new membrane with superhydrophilicity was synthesized by a facile, green, and low-cost method. First, cellulose non-woven fabric (CNWF) was modified by poly (catechin) (pCA), which has good antioxidant and antibacterial activities, to make it unaffected by ultraviolet light and to improve the stability of the structure. Then, hydrolyzed polydimethylsiloxane (PDMS) was coated on the pCA@CNWF surface via chemical bonding to make the composite hydrophobic. This durable superhydrophobic fabric can be used to separate various oil/water mixtures by gravity-driven forces with high separation efficiency (over 98.9%). Additionally, the PDMS-pCA@CNWF possesses the advantages of flexibility, high efficiency, and an outstanding self-cleaning performance, and demonstrates significant potential for applications in various environments, even under various harsh conditions, which make it very promising for the treatment of oil pollution in practical applications.