AbstractAn array of polyhedral oligomeric silsesquioxane (POSS) compounds, including metal, methacrylate, and amine functional POSS, and POSS copolymers were incorporated into aromatic and aliphatic dental resins. Heptaphenyl‐propylamine POSS and methacrylate derivatives were synthesized by corner‐capping and Michael addition reactions, respectively. The POSS compounds were tested for solubility in commercial resins at concentrations of 1, 5, 10, and 15 wt %, followed by UV polymerization of all soluble combinations. The POSS compounds generally increased modulus and had an unpredictable effect on Tg. The modulus of the aliphatic resin increased 83% by incorporation of 15 wt % aluminum‐phenyl POSS, while aromatic resins saw a maximum modulus improvement of 18% at 30°C and 72% at 160°C by incorporating 1 wt % of heptaphenyl‐methacrylate POSS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2856–2862, 2006