In the work, two linear polysiloxanes (D2V and V-3 polymers) containing vinyl (Vi) groups regularly distributed along their chains were cross-linked by hydrosilylation with Si-H groups containing polyhedral oligomeric silsesquioxane (POSS) molecules, namely: dimethylsiloxy-substituted octahedral oligosilsesquioxane (Q(8)M(8)(H)). The reactions were carried out at equimolar Si-Vi: Si-H groups ratios in methylene chloride, tetrahydrofuran and toluene in order find out the optimum solvent for achieving the highest possible polymer cross-linking levels. In toluene, cross-linking was also performed at lower reactive groups molar ratios. Investigation of the cross-linked systems allowed establishing that hydrosilylation in toluene was the most efficient. Independently of the Si-Vi: Si-H groups molar ratio in the starting reaction medium, D2V polymer reacted with Q(8)M(8)(H) to a higher extent than the V-3 one. In some systems, Q(8)M(8)(H) acted not only as a cross-linker, but also as filler. Pyrolysis of the cross-linked polymers conducted in Ar atmosphere led to formation of SiCO ceramics with high yields (63.4-85.1 wt.%). Particularly advantageous effect of incorporation of POSS molecules on ceramic yield was observed for the D2V polymer. SiCO materials obtained are pore- and crack-free and can be applied as chemically and thermally stable protective layers on various substrates. (C) 2013 Elsevier Ltd. All rights reserved.