In present paper we describe some unconventional adaptions of sol-gel method. Controlled sol-gel transformation processes of metal alkoxide based systems can lead to various novel shapes of metal alkoxide materials. Formation of different structures like tubular microstructures by gel sheet rolling, nano-and microfibres by direct drawing, as well as microtubes of metal oxides and gel dispersed liquid crystal materials are described. Different aspects of sol-gel processes leading to the formation of all of these structures are thereby discussed.