Conducting polymer – polypyrrole (PPy) microstructures were fabricated in an aqueous solution of dodecylbenzenesulfonic acid (DBSA) by electrochemical polymerization. The study implied the concentration of DBSA had great effect on the morphologies and conductivities of PPy microstructures. At lower DBSA concentration (0.2M), no obvious microstructures were generated. Increasing DBSA concentration, some novel “chayote-like”, “flower-like” microstructures were obtained by modulating electrochemical conditions. The growth process of microstructures was studied by scanning electron microscopy and relevant mechanism was discussed. Raman characterizations indicated that the microstructures were made of conductive PPy doped by DBSA.