Replication of mesoporous silica to ordered mesoporous carbon (OMC) has been studied with the recently discovered large-pore MCM-48-like cubic Ia (3) over bard mesoporous silica (KIT-6), with particular interest in the effect of the silica pore connectivity. The carbonization was performed with sucrose or furfuryl alcohol under various conditions. The resultant OMC samples were characterized by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption. The results indicate that the OMC pore structures and diameters call be systematically regulated by hydrothermal treatment of the silica template during synthesis, postsynthetic surface modification, variation of the silica source to surfactant ratio, and choice of catalysts for the polymerization of furfuryl alcohol. Thereby, the controllable range of OMC pore diameters has been increased to 13 nm from the 2-5 nm range obtained so far. Here, the most important factor is to control the pair-wise joining of enantiomeric carbon frameworks formed inside the silica template.