The importance of pyrolysis of preceramic organometallic compounds is increasing year by year as a key technology for the synthesis of new inorganic materials. According to this process, preceramic polymers are synthesized from monomer units. After cross-linking of such precursors, the obtained preceramic networks are transformed by pyrolysis into amorphous materials. Further increase of the temperature yields thermodynamically stable crystalline materials. In this paper, the general methods of the synthesis of ceramic materials based on the Si-B-C-N system via thermolysis of preceramic compounds have been reviewed. Bulk materials, coatings and fibers of such materials reveal quite interesting high temperature properties.