In recent years, wastewater treatment has become a global challenge due to growing environmental pollution. The porous deacetylated cellulose acetate (d‐CA) casting membrane was successfully fabricated by combining solution casting, pore‐forming agent leached out and deacetylation treatment. The prepared porous d‐CA casting membrane presented superhydrophilic and superoleophilic in air, oleophobic under water and superhydrophilic under oil. The water separation flux and oil separation flux of d‐CA casting membrane can go up to 23,000, and 11,500 L m−2 h−1 only under the gravity force, respectively, meanwhile it is still maintaining high separation efficiency more than 99.1%. In additionally, it has remarkable self‐cleaning capability due to its special surface wettability, it remains the high water separation flux about 18,000 L m−2 h−1 and separation efficiency of 99.1% after 25 cycles, suggesting excellent anti‐pollution capacity and reusability. The results indicate that the porous d‐CA casting membrane has a wide range of potential applications in oil/water separation, and the simple production process is expected to enable large‐scale fabrication of porous separation membranes.