Fourier transform infrared spectroscopy (FTIR) and electrical measurements were used for the characterization of the interpolymer complexation between poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) and also the ternary PAA-metal-PAAm complexes. The interpolymer complexes were prepared by adjusting the pH value of the mixture solutions at different PAA weight fractions (W-PAA). The ternary complexes were prepared by mixing metal chloride solutions (such as ErCl3 and LaCl3) with different concentrations to PAA-PAAm mixtures and adjusting the pH value for different W-PAA. It was found that the IR spectra of the interpolymer complexes showed absorption bands at shifted positions and of intensities different from those of the parent polymers. Also, the examination of the spectra of the ternary metal-polymer complexes revealed that they depend on the nature, valency, ionic radius, and concentration of the added metal chlorides. Analysis of the electrical results showed that the electrical conductivity of the interpolymer complexes are always lower than those of PAA and PAAm, which was attributed to the decrease in the mobility of the polymer chains as a result of the complexation. Also, the conductivity of the ternary metal complexes showed a dependence on the properties of the additives and were found to decrease with increasing their concentrations.