The diffusion coefficients of Triton X-100 micelles with different shape are determined by cyclic voltammetry without any probe. The first CMC (3.2 × 10−4mol-Lminus;1) and the second CMC (1.3 × 10minus;3mol-Lminus;1) of Triton X-100 micelles arc obtained, and the mechanism of electrochemical reaction for Triton X-100 is deduced, When n-hexanol is added, the diffusion coefficient of Triton X-100 micelles with different shape increases, but the solubilization fraction of n-hexanol decreases in spherical micelles and is almost constant in rodlike ones. However, the micropolarity of micelles decreases in both spherical and rodlike micelles. Furthermore, the diffusion coefficient of Triton X-100 micelles with different shape increases with temperature and the diffusion activation energy increases with n-hexanol content.