A change in surface wettability due to autogenous chemical and structural transition of electropolymerized polyaniline film is presented. A gradual increase in water contact angle of > 150 degrees on electropolymerized PANI surface was observed over the period indicated superhydrophobic surface. While an increase in the content of quinoneimine structure was observed, the surface morphology showed the formation of a dendritic structure on the aged PANI surface. Water contact angle measurement using different liquids showed the surface energy of PANI has decreased > 70% after 30 days of exposure in the ambient environment. The findings are explained based on the mechanism of self-assembled micro-nano-cluster formation over PANI surface during continuous exposure.