The nitridoborate Li4Ba[BN2]2 was synthesized from a 4:1 molar ratio of Li3[BN]2 and Ba3[BN2]2 in an arc‐welded niobium ampoule at a maximum annealing temperature of 1173 K. The structure was refined from single‐crystal X‐ray diffractometer data: new type, P1, a = 533.9(2), b = 585.0(3), c = 860.6(4) pm, α = 80.72(3), β = 73.84(6), γ = 89.87(4)°, wR2 = 0.1196, 1429 F2 values, 50 variables. The Li4Ba[BN2]2 structure contains two crystallographically independent [BN2]3– units with 134 pm B–N distance, which are slightly bent: 178° for N2–B1–N1 and 175° for N4–B2–N3. Due to the high lithium content both [BN2]3– units have a strongly distorted coordination by 8Li+ + 3Ba2+. The four crystallographically independent lithium cations show distorted tetrahedral coordination by [BN2]3– units with Li–N distances ranging from 195 to 247 pm. IR and Raman spectra show the typical vibrations of the [BN2] unit along with a well‐resolved splitting of the ν(10Β) and ν(11B) frequencies.