The effect of phenols reactivity with formaldehyde on the formation of ordered mesoporous carbons has been investigated. A strategy to accelerate the polymerization of phenolic resins by using strongly acidic conditions is proposed. The self-assembly of resorcinol-formaldehyde and block copolymers (e.g., F127) under highly acidic concentrations (e.g., 1.5 M HCl) is probably driven by the I+X-S+ mechanism and hydrogen bonding and affords a highly reproducible approach for synthesis of ordered mesoporous carbons. The synthesis can be readily scaled up with no change in sample quality. The carbon material obtained (denoted as C-ORNL-1) exhibits highly ordered hexagonal mesostructure, with a typical BET surface area of similar to 600 m(2)/g, pore size of 6.3 nm, and pore volume of similar to 0.60 cm(3)/g. One of the unique structural features of C-ORNL-1 is its high thermal stability; it can be graphitized at 2600 degrees C while considerable mesoporosity is maintained.