Free-standing films of ordered mesoporous silicon and titanium carbide-derived carbons have been synthesized using a novel soft templating approach without employing hydrofluoric acid. Tetra-Et orthosilicate or titanium citrate, alternatively, and a phenolic resin underwent an evapn. induced self-assembly yielding ordered mesoporous silicon carbide/carbon or titanium carbide/carbon composites. High temp. chlorine treatment transformed these materials conformally into carbide-derived carbons (CDC) while the ordered arrangement of mesopores was maintained. The corresponding hierarchical pore structures consist of narrowly distributed micro- and mesopores (distribution maxima at 1 and 5 nm, resp.) with a high surface area and pore vol. of up to 1538 m2/g and 2.53 cm3/g, resp. [on SciFinder(R)]