A series of trimethylsilyl end-functionalized aliphatic hyperbranched polymers has been used to template porosity in polymethylsilsesquioxane films prepared by heat treatment of a spin cast methylsilsesquioxane precursor. By varying the extent of the end-functionalization, closed pore foams with controlled pore sizes and pore contents of up to 40 vol% were obtained by chemically-induced phase separation and thermal degradation of the hyperbranched polymers during the heat treatment.