The photoluminescence (PL) and resonant Raman scattering (RRS) spectra of multiple quantum well (MQW) structures are investigated at room temperature. The spectra of Raman scattering consist of intensive band of the quantum wells luminescence and additional narrow bands. The energy shift of these additional bands was equal to the multiple value of longitudinal oscillation phonon of the strained ZnSe barriers. The intensity of these bands is resonance amplified at approaching the excitation radiation frequency to MQW luminescence bands frequency. We suppose that the given process consists of several stages: absorption of stimulating light by quantum wells; exchange of energy between hot electrons and barriers; relaxation of system including longitudinal phonon generations in barriers.