The self-assembly of tris(3-azidobenzyl)amines with 1,1,1-tris[(diphenylphosphino)methyl]ethane via tripod–tripod coupling proceeds successfully to give chiral macrobicyclic triphosphazides. The heating of these macrobicyclic cages induces a remarkable stepwise triple extrusion of molecularnitrogen to afford tri-λ5-phosphazenes, which preserved the chiral, propeller-like topology of their precursors