Sol–gel tetramethoxyorthosilicate (TMOS) derived composite thin films comprising embedded NiCl 2 nanoparticles, were illuminated and processed by 193 and 157 nm excimer laser radiation. The effect of different laser fluences of 193 nm and the number of 157 nm pulses on the material surface was studied. Atomic force microscopy imaging was used to evaluate the effects of the irradiation. It was found that surface morphology was modified in a controllable way, with physical and chemical properties strongly depending on the illumination conditions. Ablative ultraviolet laser surface processing is a generic single-step approach that can be applied successfully in composite materials. Applications involve micro/nanostructure formation for use in hybrid photonic and optoelectronic devices and other applications.