Linear oligosiloxanes functionalized with bulky side chain tris(trimethylsilyl)hexyl (TTSH) substituents were transformed into cross-linked materials by UV 193 nm excimer pulsed laser ablation. The process Occurred without any catalyst, by reactions of radicals formed in UV laser induced photolysis of side tris(trimethylsilyl)hexyl groups. Chemical changes were monitored by FTIR, LC/UV, GUMS and solubility tests. (C) 2007 Elsevier Ltd. All rights reserved.