A kind of chiral azobenzene amphiphile, N-[4-(4-dodecyloxyphenylazo)benzoyl]-L-glutamic acid (C-12-Azo-L-Glu; as shown in Fig. 1), was synthesized and the self-organization properties on solid substrates were investigated. C-12-Azo-L-Glu underwent a reversible trans-cis photoisomerization in dilute solution. While the photoisomerization was suppressed on solid substrate because of the H-aggregation, indicating the formation of compact film. When C-12-Azo-L-Glu was cast from ethanol solution onto the hydrophilic surface of mica, a stable flat-layered structure formed spontaneously in large scale. High-resolution images allowed the identification of the relative orientation of molecular rows in the ordered thin film and the crystal lattice of mica. A molecular packing model of the layered structure was proposed. There was a template effect of mica to the self-organization process. Hydrogen bonding, pi-pi interaction and the chiral center in the molecule played the important roles in the self-organization process. The cooperative competitive effect between them led to the highly ordered structure. (C) 2003 Elsevier B.V. All rights reserved.