There has been a recent revolution in high-throughput materials synthesis using automation, enabling materials to be screened and discovered at a faster rate. The acceleration of materials discovery will play a crucial role in addressing the global problems of today, particularly in relation to molecular separations, which account for 10-15% of the world's energy consumption. Porous materials have emerged as a favourable option to address such challenges, by creating systems with void spaces or pores that can be readily tailored for specific separations. Porous materials, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), porous polymers, and zeolites, have many applications as porous solids, with surface areas reaching as high as 7140 m 2 g -1 for the MOF NU-110E. Another sub-class of porous materials are porous organic cages (POCs) -discrete molecules with permanent internal cavities accessible through windows, which may pack in the solid-state to form extended porous structures, but also typically exhibit solution processibility in common organic solvents. These advantageous features have gained POCs traction in the literature for their competitive porosities and guest selectivities, along with attractive applications in catalysis, chemical sensing, in thin-film membranes for gas and molecular separations, and as porous liquids. Despite this growing interest in POCs, the targeted design and realisation of new species has been a key challenge in the field, exacerbated by the: (i) complexity of the species types that can form (i.e., thermodynamic vs kinetic products, polymeric vs discrete molecules, different cage topologies, Figure ); (ii) differing structural and thermodynamic stability of the resulting species (for example, subsequent cage catenation can occur after cage formation); (iii) packing and potential polymorphism of the individual species; and (iv) the sensitivity of the properties to all of the above.