The present invention provides for microporous ceramic materials having a surface area in excess of 50 m.sup.2 /gm and an open microporous cell structure wherein the micropores have a mean width of less than 20 Angstroms and wherein said microporous structure comprises a volume of greater than about 0.015 cm.sup.3 /gm of the ceramic. The invention also provides for a preceramic composite intermediate composition comprising a mixture of a ceramic precursor and finely divided particles comprising a non-silicon containing ceramic, carbon, or an inorganic compound having a decomposition temperature in excess of 400.degree. C., whose pyrolysis product in inert atmosphere or in an ammonia atmosphere at temperatures of up to less than about 1100.degree. C. gives rise to the microporous ceramics of the invention. Also provided is a process for the preparation of the microporous ceramics of the invention involving pyrolysis of the ceramic intermediate under controlled conditions of heating up to temperatures of less than 1100.degree. C. to form a microporous ceramic product.