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Here, we report the scalable synthesis and characterization of low-density, porous, three-dimensional (3D) solids consisting of two-dimensional (2D) hexagonal boron nitride (h-BN) sheets. The structures are synthesized using bottom-up, low-temperature (∼300 °C), solid-state reaction of melamine and boric acid giving rise to porous and mechanically stable interconnected h-BN layers. A layered 3D structure forms due to the formation of h-BN, and significant improvements in the mechanical properties were observed over a range of temperatures, compared to graphene oxide or reduced graphene oxide foams. A theoretical model based on Density Functional Theory (DFT) is proposed for the formation of h-BN architectures. The material shows excellent, recyclable absorption capacity for oils and organic solvents.