Dielectric measurements were carried out on aqueous solution of poly(diallyldimethylammonium chloride) (PDADMAC) with different concentrations at room temperature. Additionally, for selected solutions the temperature dependence of dielectric relaxation spectroscopy (DRS) was examined in the range of 5–70 °C. The dielectric relaxation in the order of around MHz was observed, and the dielectric parameters were determined from the dielectric spectra by fitting data with the Cole–Cole equation. The dielectric parameters showed strong dependences on concentration and on temperature, respectively, and these dependences are analyzed by the scaling theory. From the analysis of concentration dependence of dielectric parameters, the dielectric relaxation is assigned to the localized fluctuation of uncondensed counter-ions over the distance between chains in dilute solution and correlation length in semi-dilute solution, respectively, and the solvent quality parameter for the uncharged polyelectrolyte chain is evaluated. By the analysis of temperature dependence of dielectric parameters, we find that: the physical meanings of the typical lengths of uncondensed counter-ions are not influenced by temperature; in semi-dilute solution, the highly extended length of the chain (correlation length) increases and the end-to-end distance of the chain decreases with increasing solution temperature; in the change process of dielectric relaxation of PDADMAC solution induced by the increase of temperature, the increment of ionic diffusion coefficient and decrement of permittivity of the solvent medium are the major factors. The enthalpy and entropy of activation of the dielectric relaxation are experimentally determined by the dependence of relaxation time on temperature, individually.