For the first time, a new PL band at 1.8718 eV is observed after irradiation of Cd1-xZnxTe (x = 0.1) crystal by Nd:YAG laser at intensity 12.0 MW/cm2. The origin of this PL band we connect with formation of strongly enriched layer by Zn atoms at the irradiated surface of the sample due to a themogradient effect. Self-organizing structures of nanometer size are observed on the surface of a CdZnTe crystal (x = 0.1) irradiated by strongly absorbed Nd:YAG laser radiation at intensities 4.0-12.0 MW/cm2. The effect of exciton quantum confinement manifested by a shift to higher energies of the A0,X exciton line in the photoluminescent spectrum is present in structures of 10–15 nm in diameter at the top of nanohills. A graded band gap structure with optical window is formed on the top of nanohills.