3-Methacryloxypropyltrimethoxysilane (MPTMS) was converted to silsesquioxane oligomers by hydrolysis/condensation in three dental monomer solutions. The molecular mass distribution and molecular structures of these oligomers was studied by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Each dental monomer imparted distinct characteristics on the oligomeric silsesquioxane produced. Ethoxylated bisphenol A dimethacrylate (EBPADMA) produced low-mass oligomer silsesquioxanes that showed complete hydrolysis and a very high degree of intramolecular condensation (i.e., there were no methoxy and few silanol groups remaining on the oligomers). 1,6-Bis(methacryloxy-2-ethoxycarbon-ylamino) 2,4,4-trimethylhexane also produced fully hydrolyzed oligomeric silsesquioxanes but with twice the average molecular mass as the EBPADMA. Finally, triethylene glycol dimethacrylate produced higher mass oligomeric silsesquioxanes than EBPADMA even though it showed incomplete hydrolysis. The degree of hydrolysis increased with increasing mass, as did the degree of intramolecular condensation. Oligomers with degrees of polymerization below 8 were poorly hydrolyzed and showed little if any intramolecular condensation. Those with degrees of polymerization of 9 or greater were almost completely hydrolyzed with a high level of intramolecular condensation. (c) 2005 Wiley Periodicals, Inc.