[en] Compounds formed in the systems As-W, Se-W, Te-W, As-W-Cu, Se-W-Cu, Te-W-Cu were studied by the methods of IR and Raman spectriscopy. It is shown that they contain heteropolyanions (HPA) of the general formula [E₂W₂₁O₆₉(H₂O)]^n- and [E₂W₁₈M₃O₆₆(H₂O)₂]^n-, where E - As(3), Se(4), Te(4), M - W, Cu. A lower intensity of the bands in the range of 200-230 cm^-1 is a characteristic feature of Raman spectra of compounds of E₂W₂₁ and E₂W₁₈M₃ types, as compared with spectra of highly symmetric EM₁₂ Keggins type HPA. Vibrational spectra of HPA with different central atoms were analyzed