Recent progress in the synthesis and catalysis of silsesquioxanes and heteropolyoxoanions was reviewed. First the interesting features of silsesquioxanes were introduced as models of oxide surfaces and key components for zeolite crystallization. In addition, the catalytic properties of heteropolyoxoanions were reviewed based on our recent work about the lacunary heteropolyoxoanion as an oxidation-resistant macroligand or a mold of oxo-bridged mono- or tri-transition-metal sites.