Disclosed here is a method for making a three-dimensional micro-architected aerogel, comprising: (a) curing a reaction mixture comprising a co-sol-gel material (e.g., graphene oxide (GO)) and at least one catalyst to obtain a crosslinked co-sol-gel (e.g., GO hydrogel); (b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel (e.g., GO hydrogel); (c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure; (d) drying the wet gel to produce a dry gel; and (e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel (e.g., graphene aerogel). Also disclosed is a photoresin for projection microstereolithography, comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of a crosslinked co-sol-gel.