Dipole potential is the potential difference within the membrane bilayer, which originates due to the nonrandom arrangement of lipid dipoles and water molecules at the membrane interface. Although dipole potential is generally used in the context of bilayer membranes, the nonrandom arrangement of amphiphiles and water dipoles would also contribute to dipole potential in organized molecular assemblies such as micelles. In this work, we show that the process of micelle formation from monomers for a representative variety of detergents is associated with dipolar rearrangement. We monitor the dipolar reorganization upon micellization as a change in dipole potential, measured by the dual wavelength ratiometric approach utilizing the potential-sensitive membrane probe di-8-ANEPPS. We further utilized this phenomenon to estimate the critical micelle concentration (CMC) of a variety of detergents. CMC determined by this method are in overall agreement with the literature values of CMC for these detergents. To the best of our knowledge, these results constitute the first report showing dipolar reorientation during micellization. We conclude that dipole potential measurements could provide a novel approach to explore micellar organization.