Aligned micro-ribbons of N-chiral alkyl substituted polypyrrole have been grown for the first time by electrochemical polymerization of methyl (S)-(+)-2-(1H-pyrrol-yl) propionate (1) and methyl (S)-(-)-3-phenyl-2-(1H-pyrrol-yl) propionate ( 2) in acetonitrile containing tetrabutylammonium perchlorate (TBAClO(4)) and camphor-10-sulfonic acid (CSA) enantiomer. The micro-ribbons stand upright on the working electrode surface in a high density. They have a length of 100-200 mum, a width of 20-50 mum and a thickness of 3-5 mum. Scanning electron microscopic (SEM) studies showed that the micro-ribbons were assembled by nanometer balls with diameters of 30-50 nm. A hole growing mechanism was suggested according to the SEM pictures recorded during the electrochemical growth process. The structures of the resulting polymers have been characterized by infrared and Raman specroscopies. (C) 2004 Kluwer Academic Publishers.