We report the synthesis of a new class of materials called periodic mesoporous dendrisilicas. They are prepared from dendrimers with trialkoxysilyl groups at the outmost shell. Dendrimers of various cores and numbers of shells are used. The dendrisilica synthesis is based on acid- or base-catalyzed hydrolysis of the trialkoxysilyl groups and subsequent template-directed condensation of the dendrimers into an ordered template-dendrisilica nanocomposite. The template can be removed with organic solvents, producing a periodic mesoporous dendrisilica whose pore walls consist of interconnected dendrimer building blocks.