Both intermolecular and intramolecular motions of concentrated aqueous KSCN solution were investigated by means of femtosecond optical heterodyne-detected Raman induced Kerr effect spectroscopy (OHD-RIKES) and Raman spectroscopy. We found that all concentrated aqueous KSCN solutions present significantly large anisotropic hyperpolarizabilities in their femtosecond OHD-RIKES measurements, which is attributed to a 45cm −1 librational motion of SCN − . We also found that the weakening of the 170cm −1 stretching motion of water intermolecular hydrogen bond (HB) by 0.10m (molality) KSCN is equivalent to that by 4.00m KBr in aqueous solution, which implies SCN − strongly distort the HB network of water. Besides, we found that the rotational relaxation time constant of SCN − increases with the increase of KSCN concentration in aqueous solution, which is correlated with the corresponding viscosity of respective aqueous KSCN solution.