Photon counting histogram (PCH) analysis is a statistical method that provides independent information about the relative brightness and the number of molecular entities in the system. This suggests that it could be very advantageous in the analysis of intermolecular interactions in multicomponent systems. In this paper we employ PCH to study the interaction of Rhodamine 6G (Rh-6G) with sodium dodecyl sulfate (SDS) micelles and show how the method can unveil the mechanism of quenching of Rh-6G by methyl viologen (MV).