Molecular aggregation plays a key role in the physicochemical properties of dyes and surfactants. In this work, we show that electrical impedance spectroscopy (EIS) provides a practical method for the investigation of processes such as micellization in surfactants and dye dimerization. The electrical characterization of the structural phase transitions associated with aggregation events in these systems allows an accurate and direct determination of relevant parameters such as the corresponding critical concentrations for micelle formation and dimerization of these types of molecules, without the need of recurring to the use of auxiliary probe or reporter molecules. Because of its competitive advantages with respect to currently used methods (such as conductimetry and spectroscopic techniques), we argue that when implemented along the procedures described in this work, EIS becomes a simple and convenient technique for the characterization of aggregation processes in soft matter.