Raman spectroscopic investigation of the vibrational and orientational relaxation of non-associated anions of the type of spherical top, ClO−4,SO2−4,PO3−4 (Td symmetry), symmetric top, NO−3,CO2−3 (D3h), and the linear NCS− ion (C∞ν) was made in dilute aqueous solutions in the temperature range 293–363 K. The times of vibrational, τν, and orientational, τ2R, relaxation, and the activation energy of the orientational motion of anions, were calculated. It is shown that the main mechanism for the orientational relaxation of anions is vibrational dephasing which does not lead to the destruction of the hydrate shells of the anions. The reorientation of ClO−4,SO2−4,NO−3,CO2−3 anions occurs through a rotational diffusion mechanism while for NCS− jump diffusion takes place. It is established that the reorientation of ClO−4,NO−3 and NCS− anions is associated with the destruction of the ion-molecular hydrogen bond.