Femtosecond spectroscopy was applied to study the ultrafast relaxation dynamics for the excited state of xanthogenate Ni(S 2 COEt) 2 complex in acetonitrile and CCl 4 . The radiation of second harmonic (400nm) of Ti:Sapphire laser transfers the Ni(S 2 COEt) 2 complex to excited LMCT state which in CCl 4 with time 0.76ps decays to excited triplet state of (d,d*) type. With the time 6.8ps the triplet state undergoes vibrational relaxation and then it slowly decays during 550ps to the ground state. In acetonitrile the processes of relaxation after femtosecond excitation follow the same pathway with a close times.