The thermal characterization of the polyelectrolyte complexes (PEC) was investigated by thermogravimetric analysis (TGA) and dielectric analysis (DEA). In the results of the DEA, two relaxation peaks appeared around 50 and 180°C in the sample, CSHA11. The relaxation peak of all samples increased the temperature because of an increase in the number of chitosan segments in the PEC films. The activation energy of the relaxation process was obtained by performing a linear least squares analysis (Arrhenius plot) on the plot of ln(frequency) vs. 1/T max, where T max is the temperature which corresponds to the loss factor peak maximum at various test frequencies using the Arrhenius equation. The thermal decomposition and thermal stability of hyaluronic acid (HA), chitosan, and PEC films were investigated using TGA.