Poly(hydroxymethylsiloxane) (PHMS) has been synthesized by selective oxidation of poly(methylhydrosiloxane) (PMHS) with a dimethyldioxirane solution in acetone. PHMS synthesized in situ showed no tendency for self-condensation to siloxane in solution when the concentration of PHMS was less than 1% (g/mL). PHMS gave ceramic materials at 79% yield at 700 degrees C in a nitrogen atmosphere. Miscibility studies of PHMS with a variety of organic polymers by solution-cast films showed that organic-inorganic polymeric hybrids were formed for poly(N-vinylpyrrolidone) (PVPr), poly(ethyloxazoline) (PEOx), and poly(4-vinylpyridine) (PVPy). The hydrogen-bonding interactions in these hybrids were investigated by FT-IR spectroscopy.