Organic microporous materials based on silicon-containing spiroketal and spirothioketal polymers were synthesized via a 1,3-dioxol-forming polymerization reaction between 1,1a,4,4a,5,5a,8,8a-octahydro-2,3,6,7-tetra(trimethylsilyl)-9,10-anthraquinone and different types of polyol or polythiol. These silicon-containing polymers were subjected to bromination to yield bromine-containing polymers. The structures of the prepared polymers were confirmed by NMR spectroscopy and molecular mass measurements. Nitrogen adsorption/desorption isotherms of the prepared polymers showed that a large amount of nitrogen was adsorbed at low relative pressure, indicating microporosity. These polymers have BET surface areas in the range of 505-830 m(2) g(-1). These polymers were determined to be useful for pervaporation separation of phenol/water mixtures.