Two novel ternary air-stable transition-metal carbodiimides, MnHf(NCN) 3 and FeHf(NCN) 3 , were synthesized via solid-state metathesis using either ZnNCN or Na 2 NCN as the carbodiimide source and the corresponding binary metal chlorides. These two phases are the first examples of transition-metal carbodiimides with an AB(NCN) 3 composition, akin to ubiquitous ABO 3 perovskite oxides. The crystal structure of MnHf(NCN) 3 was determined and refined from powder X-ray diffraction (XRD) data in the non-centrosymmetric space group P6 3 22 allowing for chirality, the assignment of which is supported by second-harmonic generation (SHG) measurements. FeHf(NCN) 3 was found to crystallize isotypically, and the presence of iron(II) in a high spin state was confirmed by 57 Fe Moßbauer spectroscopy. The structures are revealed to be NiAs-derived and can be described as a hexagonal stack of NCN 2− anions with metal cations occupying 2/3 of the octahedral voids. Both IR spectroscopic measurements and DFT calculations agree that the NCN 2− unit is a bent carbodiimide with C 2v symmetry, necessary to account for the size difference present in such a vacancy-ordered structure. Magnetic studies reveal predominantly strong antiferromagnetic interactions but no long-range order between the paramagnetic Mn 2+ centers, likely due to the dilution of Mn 2+ over the octahedral sites or perhaps even due to some degree of magnetic frustration. The optical and electrochemical properties of MnHf(NCN) 3 were then studied, revealing a wide band gap of 3.04 eV and p-type behavior.