Dynamics of nanostructures (nanocones and nanocavties) formation on surface of semiconductors by laser radiation based on Thermogradient effect (TGE) is studied. Nanostructures formation of both nanohills and nanocavities are explained by point defects redistribution in gradient of temperature at the irradiated surface. Study of photoluminescence (PL), atomic force microscopy (AFM) and Raman back‐scattering spectra speak in favour of presence of quantum confinement effect (QCE) on the top of nanocones on the irradiated surface of semiconductor single crystals. Aggregation of vacancies under the irradiated surface forms nanocavities. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)