The vibrational and reorientational motions of H(2)O ligands and NO(3)(-) anions were investigated by Fourier transform middle-infrared Raman scattering (RS) spectroscopy and phonon density of states, calculated from incoherent inelastic neutron scattering, in the high- and low-temperature phases of [Ca(H(2)O)(4)](NO(3))(2). The theoretical IR and RS spectra were also calculated by means of the quantum chemistry method using density functional theory with PBE1PBE functional at 6-311++G(2d,2p) basis set level. The temperature dependences of the full width at half maximum values of nu(s)(H(2)O) bands in both the infrared absorption and the RS spectroscopy suggest that the observed phase transitions (at T(C1) and T(C2)) are not connected with a drastic change in the speed of H(2)O reorientational motions. However, similar Raman nu(4)(NO(3)(-)) band shape measurements as a function of temperature revealed the existence of a fast NO(3)(-) reorientation in phase I, which is abruptly slowed at the phase transition at T(C1). Activation energy values for the reorientational motions of H(2)O ligands and NO(3)(-) anions were calculated.