A hybrid organic-inorganic material derived 3- (glycidoxypropyl)-trimethoxysilane (GPTMS) and fullerene derivatives has been developed for optical limiting applications. The control of the final material has been achieved by engineering the matrix-fullerene solid-state system. Different Lewis acids (Zr(OBut)4, Ti(OBut)4, BF3, SiCl4, and TiCl4) have been used as the catalysts of the epoxy ring opening of (GPTMS) and the polyethylene oxide formation, in three different syntheses, to control and optimize the matrix- fullerene interaction and the optical limiting properties. The microstructure of the hybrid matrix has been studied by Fourier Transform Infra-Red Spectroscopy. UV-vis spectra and optical limiting measurements of the doped materials showed that in the Zr(OBut)4, TiCl4, BF3 derived matrices clustering of fulleropyrrolidine molecules is avoided and optical limiting is obtained. In the Ti(OBut)4, SiCl4, and not epoxy catalyzed derived matrices, instead, the aggregation of fulleropyrrolidines degraded the optical limiting properties. The laser damage threshold in the Zr(OBut)4, TiCl4 and especially BF3 derived matrices was larger than in the other matrices. Moreover, a multilayer system has been fabricated to develop an optical limiting device.