The frequency-dependent dielectric properties and conductivity of partially quaternized polysulfones, quaternized polysulfones containing chelating groups, and chelated quaternized polysulfones with Cu2+ have been studied. The permittivity has low values and is dependent on the chemical characteristic of samples, in relation with the charge transfer complex and free volume and, consequently, with packing of the polymer chains and of the polarizable groups per volume units. At temperatures below 150 °C, all polysulfone films develop two relaxation processes, i.e., γ and β relaxation, involving different enthalpy and entropy contributions induced by their chemical structures. Frequency–temperature-dependent conductivity showed that conductivity increased with frequency, while the values of thermal activation energy of electrical conduction, lower that 1, suggest that a model based on energy bandgap representation could be suitable for explaining the temperature influence on AC conductivity for all samples. In addition, enhancement of mobility of the charge carrier upon complexation was observed for chelated quaternized polysulfones with Cu2+. All these typical semiconducting properties recommend the studied polymers as potential candidates for use in various applications in electrotechnical industry.