Microcellular polysiloxane monoliths were prepared from the continuous phase of a concentrated inverse emulsion. The formulation of the material was adapted to obtain monoliths having structural properties similar to those of common poly(styrene-co-divinylbenzene) polyHIPEs. The network was generated by hydrosilylation reaction between a vinylsiloxane crosslinking agent and an oligomeric hydrogenosiloxane. The solids obtained were characterized by mercury porosimetry, nitrogen sorption, and SEM. (c) 2007 Wiley Periodicals, Inc.