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. Tetraethyl orthosilicate or titanium citrate, alternatively, and a phenolic resin underwent an evaporation induced self-assembly yielding ordered mesoporous silicon carbide/carbon or titanium carbide/carbon composites. High temperature 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, respectively) with a high surface area and pore volume of up to 1538 m ²/g and 2.53 cm ³/g, respectively.