We present a study of fluorescence (5-250)K and FTIR spectra of poly(di-n-hexylsilane) incorporated into nanoporous silicas (MCM-41 and SBA-15 types) and SiO2 aerosil. It is shown that the essential local conformation change of the polymer chain occurs only for the polymer embedded into and oriented in small-diameter pores with a large number of Si-OH groups on the surface of the walls. The competition between the polymer-surface and the polymer-polymer interactions leads to the restructuring of a polymer incorporated into the large pores of SBA-15 where the separarate polymer chain having trans- and gauche-conformations as well as the aggregates can be found. The presence of the gauche-conformation is confirmed by the shift of CH2a and CH2s stretching vibrations and, additionally, by the redistrubution of their intensity with increasing the pore diameter. (c) 2007 Elsevier B.V. All rights reserved.