Abstract Numerous metalla‐supramolecular architectures have been designed using coordination‐driven self‐assembly, while the number of analogous organic architectures is still very limited. In this regard, mainly di‐, tri‐ and a few tetra‐aldehydes have been exploited as precursors in combination with appropriate di‐/tri‐amines to obtain the desired structures with limited complexities. We report here facile synthesis of two face‐directed tetrahedral organic cages ( TC‐R and TC‐S ) that were formed by [4+12] imine condensation of a new hexa‐aldehyde precursor with two enantiomers of 1,2‐diaminocyclohexane separately ( CA‐R and CA‐S ). The covalent imine cages are very large with an intrinsic porous cavity of ∼1250 Å 3 and the faces of the cages consist of aromatic aldehyde units whereas each corner is occupied by three semi‐flexible diamine moieties. Palladium (PdNPs) nanoparticles (3.5±0.3 nm) were synthesized employing the cage TC‐R as a solid support via double‐solvent approach. Furthermore, the cage hosted PdNPs [ Pd(0)@TC‐R‐A ] exhibited efficient catalytic activity for selective homocoupling of aryl‐ and hetero‐aryl halides with high thermal stability and reusability.