Etching polymer-derived silicon-oxycarbide ceramics with hydrofluoric acid creates nanoporous structures of specific surface areas as high as 600 m(2)/g. The change in composition upon etching shows the removal of silica, not carbon. The structure remaining after etching is postulated to consist of a scaffolding of graphene networks with their surfaces decorated with mixed bonds of tetrahedral silicon bonded to both oxygen and carbon (SiOmC4-m, where m=1, 2, or 3). The pores existing within such scaffoldings are presumed to have been filled with SiO2 tetrahedra, which are removed by etching. The measurement of the average pore size and pore volumes permits us to estimate the width of the graphitic domain walls, delta(W), left behind by the etching process. The smallest value of delta(W), which corresponds to the specimen with the highest surface area, is approximately 1 nm, which is about equal to the total width of one graphene layer and two SiOmC4-m tetrahedra, one on either side of the graphene sheet. This highest surface area specimen is also believed to have the largest size of the silica domains in the unetched samples. In specimens with smaller domains, the etching is only partially successful in removing the silica, presumably because their small size hinders the access of the etchant to the silica tetrahedra. The above behavior is found for samples with low to moderate carbon content. In one sample with a very high carbon content, the etching process removes some carbon as well as silica.