Polymeric metal complexes were synthesized mechanochemically by ultrasonic action on mixtures of poly(ethy1ene terephthalate), ethylenediamine, and vanadium trichloride or by vibratory milling of a mixture of poly(e-caprolactam) and manganese dichloride (MnCI, . 4H,O).The influence of duration of ultrasonic action or vibratory milling as well as the ratio of reagents on the efficiency of complexation was studied. The resulting products were characterized spectroscopically (by IR and ESR spectra), by elemental analyses, and by X-ray diffraction. They show a relatively high thermostability and semiconductivity.