To facilitate the recycling and reuse of cigarette filters and oil/water separation, a superhydrophobic cigarette filter was made by coating with dodecanethiol-modified polypyrrole (Ppy) particles by a dip-coating method. SEM, FTIR, and XPS were used to analyze the surface morphology and chemical compositions. The as-prepared superhydrophobic cigarette filter can realize wettability alteration via changing the ammonium persulfate (APS) concentration from 0.15 mol/L to 3 mol/L, and the contact angle increased from 0° on the original cigarette filter to 155° with a sliding angle of 5°. The superhydrophobic cigarette filter could effectively separate various oils and organic solvents. The separation efficiency was 98.8% and the separation stability was good. Furthermore, the as-prepared superhydrophobic cigarette filter had a large oil absorption range and could absorb different oils and organic solvents, including petroleum ether, engine oil, vegetable oil, n-hexane, and chloroform, with maximum absorption capacities ranging from 9.4 g/g to 22.7 g/g. According to the above results, we believe that the as-prepared superhydrophobic cigarette filter should have great potential in the recovery of solid waste and high-efficiency oil/water separation.