A method for obtaining hierarchically structured porous carbons, employing 3D printing to control the structure down to the lower μm scale, is presented. To successfully 3D print a polymer precursor and transfer it to a highly stable and structurally conformal carbon material, stereolithography 3D printing and photoinduced copolymerization of pentaerythritol tetraacrylate and divinylbenzene are employed. Mechanically stable structures result and a resolution of ≈15 μm is demonstrated. This approach can be combined with liquid porogen templating to control the amount and size (up to ≈100 nm) of transport pores in the final carbonaceous material. Additional CO2 activation enables high surface area materials (up to 2200 m2 g-1) that show the 3D printing controlled μm structure and nm sized transport pores. This unique flexibility holds promise for the identification of optimal carbonaceous structures for energy application, catalysis, and adsorption.