Hybrid organicinorganic materials can organize into layered crystalline structures through self-organization when bridged silsesquioxanes are used in the solgel synthesis. Crystallization is, however, also observed in hybrid materials when 3-glycidoxypropyltrimethoxysilane is left to react in highly basic conditions; this synthesis route shows a peculiar property which is the possibility of preparing also crystalline hybrid films by controlling the solgel process. The crystalline films exhibit optical anisotropy and are optically transparent. In this article we briefly review the main achievements of our research group in the field.