A new polymeric precursor, perhydropolysiloxazane (PSNO), for silicon oxynitride (SiON) ceramic was synthesized by a simple one-pot procedure involving partial hydrolysis of H(2)SiCl(2) and the following ammonolysis reaction of the hydrolyzed intermediates with NH(3). The structure of new polymer was characterized with perhydropolysiloxane (PHSO) and perhydropolysilazane (PHSN) as reference substances. The conversion of PSNO to ceramic was investigated by TGA, FT-IR, and solid (29)Si-NMR analyses. A Si-rich Si(2)N(2)O ceramic was produced upon pyrolysis of PSNO at 1400 degrees C under N(2) atmosphere. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1094-1099, 2012