©2015 Optical Society of America. Spectroscopic characterization of Fe:ZnSe(Cr:ZnSe) crystals under visible excitation into the charge transfer bands of Transition Metal ions were studied. The excitation efficiencies of mid-IR photoluminescence between 5T2(5E) and 5E(5T2) states via direct relaxation to the upper laser levels and via metastable upper 3T1 were investigated. It was demonstrated that the latter route is the dominant process for Cr2+ ions and could provide sufficient pump rate for mid-IR lasing. The pump efficiencies via direct relaxation to the upper laser levels were estimated to be <2% for both ions under 532 nm excitation wavelength.