Finite control of pore size distributions is a highly desired attribute when producing porous materials. While many methodologies strive to produce such materials through one-pot strategies, oftentimes the pore structure requires post-treatment modification. In this study, modulation of pore size in cobalt-silica systems was investigated by a novel, non-destructive, self-templated method. These systems were produced from two cobalt-containing silica starting materials which differed by extent of condensation. These starting materials, sol (SG') and xerogel (XG'), were mixed with pure silica sol to produce materials containing 5-40 mol% Co. The resultant SG-series materials exhibited typical attributes for cobalt-silica systems: mesoporous characteristics developed at high cobalt concentrations, coinciding with Co3O4 formation; whereas, in the XG-series materials, these mesoporous characteristics were extensively suppressed. Based on an examination of the resultant materials a mechanism describing the pore size formation and modulation of the two systems was proposed. Pore size modulation in the XG-series was caused, in part, by the cobalt source acting as an autogenous template for the condensation of the silica network. These domains could be modified when wetted, allowing for the infiltration and subsequent condensation of silica oligomers into the pre-formed, mesoporous cages, leading to a reduction in the mesoporous content of the final product.