Polyaniline (PANI), a typical organic photocatalyst, has an adjustable structure and good stability, can be easily synthesized on a large scale, and is economical. PANI is doped with ions to regulate its internal structure and improve its photocatalytic performance. However, its photocatalytic performance is limited by the doping concentration and its intrinsic properties, hindering its further application. Herein, PANI films with a piezo‐photocatalytic function are fabricated to improve photocatalytic performance and explore their self‐powered environmental purification property. PANI/poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) sandwich films, with PVDF‐HFP as the interlayer, are prepared by introducing a piezoelectric field into PANI photocatalysts, thereby achieving excellent piezo‐photocatalytic performance. The as‐fabricated piezo‐photocatalyst degrades methyl orange at a rate of 91.2% after 60 min under magnetic stirring. Owing to the low Young's modulus of the all‐organic catalyst, self‐powered purification is realized using the PANI/PVDF‐HFP film. Leaf surfaces are functionalized by loading the film in them for removing pollutants under sunlight and water flow. Thus, this study proposes a common strategy, wherein a piezoelectric interlayer is introduced to load the organic photocatalyst for preparing an all‐organic piezo‐photocatalyst. This piezo‐photocatalyst can be easily recycled and responds to weak forces, realizing its application for self‐powered environmental purification.