Three-dimensional (3D) graphene-based macrostructures (GBMs) have shown great potential in a wide range of clean energy-related technologies (including batteries, supercapacitors, fuel cells, solar cells, etc.) and environmental remediation applications (such as absorption, adsorption, catalysis, sensors, etc.) during recent years. However, from a practical viewpoint, a fundamental understanding of the structure–property relationship of 3D GBMs is essential to precisely tune their physicochemical properties, thereby outspreading their application potential. The current chapter targets this aspect amongst others, with a special emphasis on the effects of pore geometry on the physicochemical properties of 3D GBMs.