Abstract: The reactions Ca(~1S_0)+ CH_2Cl_2, CHCl_3 and Ca(~3P)+ CH_2Cl_2, CHCl_3 were studied by means of the laser induced fluorescence (LIF). Systematic simulation of the observed LIF spectra revealed that change of the Ca atoms from the ~3p states to the ~1S_0 state brought about a decrease of the fraction of total energy going to the ground state CaCl product vibration and an increase of the fraction of total energy going to the ground state CaCl product rotation. Total cross sections for the reactions of Ca(~1S_0)+CH_(4-n)Cl_n(n=2, 3) and the fraction of the Ca atoms going to the ~3P states in the discharge Ca beam were estimated from the LIF indensity of the CaCl product and total cross sections for the reactions Ca(~3P)+CH_(4-n)Cl_n. They are 0.39±2 nm, 0.45±2 nm, 1.8+0.1%, respectively.