Micro/nano-structures of salicylic acid (SA) doped polyaniline (PANI) deposited on a glass substrate were prepared by a template_free method associated with a deposition process.It is found that the morphology and wettability of the PANI-SA deposited on the substrate are affected by the molar ratio of dopant to aniline (An) and deposition time.A highly hydrophobic surface with a water contact angle of 148°is constructed by the co-existence of microspheres and nanofibers prepared at the reaction time of 60 min and［SA］/［An］= 1∶1. It originates from the contribution of the air trapped in the inter-space of rough surface aggregated by micro/ nano-structures.The molecular structure characterized by FTIR and UV-Visible shows that the product obtained in the initial stage of polymerization is oligoaniline

while the finial product is identical to the emeraldine salt form of PANI.