Analysis of the vibrational and orientational relaxation of polyatomic anions, referring to the type of spherical top СlО₄⁻, AsF₆⁻, PO₄3; SO₄2;⁻, and of symmetrical top CF₃SO₃⁻, SO₃2;⁻, NO₃⁻, HPO₄2;⁻ in aqueous solutions according to the Raman spectroscopy data is presented. It is demonstrated that the anion-cation interaction results in a considerable decrease of the vibrational relaxation time and in changingof phase modulation mechanism. The conclusion that the formation of the ion-molecular H-bond and theinteraction of anions with cations is concluded to lead to hindering of the anion orientational motion is drawn.