In summary, we have achieved the complete oxidation of 1 to access the new tetrahedral, tetravalent inorganic scaffold 2 that shows high thermal, air, and redox stability due to its unique cage geometry. Despite the robustness of its core, 2 remains amenable to coronal decoration as shown by metathesis reactions yielding four-fold extended molecular constructs such as 3 and new classes of inorganic network materials such as 5. The latter is unprecedented as the first porous framework made exclusively from P=N/P-N bonds. These results provide proof-of-principle that a rich molecular or macromolecular covalent chemistry may be built upon this phosphaza-adamantane scaffold, which moreover benefits from the practical convenience of a 31 P NMR spectroscopic handle to accelerate analysis in either the solution or solid phases. Investigations into more expeditious syntheses of 2, its use as a precursor to new inorganic materials, and applications as a secondary bonding unit in crystalline reticular chemistry are underway.