Variation of fluorescence background in the Raman spectrum was investigated versus laser power, which was measured on Cd0.96Zn0.04Te surface at low temperatures. The fluorescence signals “burning out” were observed, accompanied by a red shift of the material's phonon peaks. It was shown that the “burning out” of the fluorescence signals was correlated to the transformation of the crystal surface structure, which was directly indicated by the red shift of the phonons. The exciting laser should be responsible for the structure transformation.