Polypyrrole (PPy) is a promising conductive polymer (CP) with electrical versatility, easy synthesis and functionalization, stability, and biocompatibility. Diverse architectures have been adopted to improve PPy performance, but the direct and precise patterning of various architectures remains challenging. Here, the unique formation of a PPy membrane on the air/water interface of a droplet solution containing ammonium persulfate and phytic acid is investigated. When a PPy thin film forms on the air/water interface, the top of the droplet rapidly flattens. The formation procedure and final structure of the PPy thin film are visualized and quantitatively investigated. Unlike the typical globular structure of PPy, the self‐assembled PPy film surface fabricated in this study is very organized and regularly shaped. This well‐ordered membrane may have a very high buckling strength greater than the surface tension of the solution. The proposed precise fabrication method is simple and inexpensive for fabricating patterned functional membranes. These results provide new insight into the fabrication of CP and their applications in various practical electromaterial engineering fields. The unique formation of polypyrrole (PPy) thin film on the air/water interface of a droplet solution containing ammonium persulfate and phytic acid is investigated. The self‐assembled PPy film surface is very organized and regularly shaped. Considering that the precise patterning of various architectures hinders the design of conductive polymers, the proposed method is inexpensive and simple for fabricating patterned functional membranes. [ABSTRACT FROM AUTHOR]