The Li+ ion conductor Li27−x[P4O7+xN9−x]O3 (x≈1.9) has been synthesized from P3N5, Li3N and Li2O in a Ta ampoule at 800 °C under Ar atmosphere. The cubic compound crystallizes in space group
with a=12.0106(14) Å and Z=4. It contains both non‐condensed [PO2N2]5− and [PO3N]4− tetrahedra as well as O2− ions, surrounded by Li+ ions. Charge neutrality is achieved by partial occupancy of Li positions, which was refined with neutron powder diffraction data. Measurements of the partial ionic and electronic conductivity show a total ionic conductivity of 6.6×10−8 S cm−1 with an activation energy of 0.46±0.02 eV and a bulk ionic conductivity of 4×10−6 S cm−1 at 25 °C, which is close to the ionic conductivity of amorphous lithium nitridophosphate. This makes Li27−x[P4O7+xN9−x]O3 an interesting candidate for investigation of structural factors affecting ionic conductivity in lithium oxonitridophosphates.