Microporous silicas with pore sizes in the range intermediate between traditional microporous and mesoporous materials have been synthesized by using dodecyldimethylbenzylammonium chloride as a template. These microporous silicas can be synthesized by either acidic S+X-I+ or basic S+I- assembly pathways and consist of disordered channels with almost identical pore sizes of 12.2 Angstrom in both cases. Their BET surface areas are larger than 1000 m(2)/g after being calcined in air.