The mixed‐valence europium tantalum nitride oxide EuIIEuIII2Ta2N4O3 was synthesized with the ammonothermal approach in high‐pressure custom‐built autoclaves. The reaction was performed at 1070 K and a maximum pressure of 170 MPa in an ammonobasic environment with NaN3 and NaOH as mineralizers. EuIIEuIII2Ta2N4O3 was obtained as a black microcrystalline powder. Single‐crystal synchrotron diffraction data revealed a Ruddlesden‐Popper phase crystallizing in space group P42/mnm (no. 136) with a = 5.7278(1), c = 19.8149(5) Å and Z = 4. The crystallographic results from single‐crystal diffraction data have been confirmed by powder diffraction and TEM measurements. Anion positions were assigned to O and N based on bond‐valence (BVS), lattice energy (MAPLE) and charge distribution calculations (CHARDI). EuII and EuIII are crystallographically ordered. The band gap was estimated from UV/Vis measurements employing the Kubelka–Munk function to be 0.6 eV, which supports the black color and the mixed valence of europium.