Pyridine-catalyzed reactions of methyldichlorosilane with bis(trimethylsilyl) carbodiimide afford a dichlorosilane-derived anhydrous sol-gel material. Both trimethylchlorosilane formation and Si-H disproportionation act as crosslinking mechanisms. The dried gels form amorphous or crystalline materials, depending on the sample history. The xerogels gave Si/C/N ceramics when pyrolyzed at 1200 degrees C, Copyright (C) 1999 John Wiley & Sons, Ltd.