Urchinlike nanostructure of well-defined Sb(2)S(3) crystals of 3-4 μm in length and 30-150 nm in diameter oriented along [001] direction have been produced at a mild reaction temperature of 90 °C from SbCl(3) and S-methyl 3-phenyldithiocarbazate [C(6)H(5)NHNHC(S)SMe] in ethylene glycol medium. During the reaction, the amorphous Sb(2)S(3) spheres of 1.4 μm in diameter were formed at early reaction stage and then crystalline nanorods were continuously grown at the surface of Sb(2)S(3) spheres while transforming their morphology into urchinlike structure. The urchinlike Sb(2)S(3) was composed of single-crystalline Sb(2)S(3) nanorods, belong to the orthorhombic phase with cell parameters a = 11.307 Å, b = 11.278 Å, c = 3.847 Å and absorbed the light up to 750 nm-wavelength region. The urchinlike Sb(2)S(3) architecture was applied to the photoelectrochemical cell.