Conducting hybrid submicrostructures composed of chitosan (CS) and silica-based conducting poly [N-(3-trimethoxysilylpropyl)aniline] (PTMSPA) were prepared by graft copolymerization. The spherical and fibrous morphologies of the CS-PTMSPA hybrid submicrostructures could be observed by optical and field emission electron microscopy. Under room temperature conditions, the CS-PTMSPA graft copolymers possessed the uniformly distributed spherical submicroparticles with diameters in the range of ca. 400-1,000 nm. On the other hand, under ice cold conditions (5 ºC), CS-PTMSPA showed the development of randomly oriented fiber bundles. The diameter of a single fiber was in the range of ca. 100-500 nm. These CS-PTMSPA fibers were obtained by a temperaturedriven template-free self-assembly pathway. Spectroscopic and thermal evaluations confirmed that CS-PTMSPA graft copolymer had been prepared by an oxidative polymerization method. The electrochemical performance of the CS-PTMSPA submicrostructures were compared with CS and PTMSPA by cyclic voltammetry with the Fe(CN) 6 3-/4-system as a redox marker. The CS-PTMSPA submicrostructures showed high electrical conductivity (difference between the anodic and cathodic peaks = 0.24 and 0.29 V for CS-PTMSPA sphere and fiber, respectively) compared to those of CS (0.14 V) and PTMSPA (0.20 V), which was ascribed to the relatively high surface-to-volume ratios of these submicrostructures.