An ordered honeycomb structure of 4-dodecylbenzenesulfonic acid (DBSA)-doped polyaniline (PANI) is fabricated in a humid atmosphere. By controlling both the relative humidity in the atmosphere and the concentration of the conducting polymer, different morphologies of the honeycomb structure can be obtained. The driving force of this procedure is capillary force (self-assembly), and water droplets serve as a template. Furthermore, the honeycomb structure film of PANI-DBSA is proved to be electroactive and exhibits semiconducting properties in the appropriate doping state.