Hierarchically porous materials are becoming increasingly important in catalysis, separation, and energy applications due to their advantageous diffusion and flux properties. Here we present the synthesis of hierarchically macro- and mesoporous carbon materials with graded porosity from a one-pot fabrication route. Organic-polymeric hybrids of a carbon precursor and poly(isoprene)-block-poly(styrene)-block-poly(4-vinylpyridine) with graded porosity are obtained via coassembly and nonsolvent-induced phase separation. The membranes were carbonized at temperatures as high as 1100 °C with simultaneous decomposition of the block copolymer. The carbon materials show an open nanoporous top surface with narrow pore-size distribution that opens up into a graded macroporous support with increasing macropore size along the film normal and mesoporous walls, providing for highly accessible porosity with a large surface area of over 500 m2 g-1. Further, we expand the direct synthesis process to form well-dispersed metal nanoparticles (such as nickel and platinum) on the graded, hierarchically porous carbon materials. Our one-pot synthesis offers a facile approach to graded macro- and mesoporous carbons.