Amorphous selenium (a-Se) is the simplest model material for investigation of the well-known photoinduced structural and optical transformations in amorphous chalcogenides. Since a lot of parameters and characteristics of materials essentially change at nanoscale, we applied nanostructuring to a-Se in nanomultilayers, obtained by pulsed laser deposition. The enhancement of photo- and thermally-induced crystallization was observed in a-Se/aluminosilicate nanomultilayers due to the initially heterogeneous state of Se in such samples, in comparison with single a-Se layers. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.