The structural variability of a compound class is an important criterion for the research into phosphor host lattices for phosphor-converted light-emitting diodes (pc-LEDs). Especially, nitridophosphates and the related class of imidonitridophosphates are promising candidates. Recently, the ammonothermal approach has opened a systematic access to this substance class with larger sample quantities. We present the successful ammonothermal synthesis of the imidonitridophosphate Ba4P4N8(NH)2:Eu2+. Its crystal structure is solved by X-ray diffraction and it crystallizes in space group Cc (no.9) with lattice parameters a=12.5250(3), b=12.5566(4), c=7.3882(2)Å and β=102.9793(10)°. For the first time, adamantane-type (imido)nitridophosphate anions [P4N8(NH)2]8- are observed next to metal ions other than alkali metals in a compound. The presence of imide groups in the structure and the identification of preferred positions for the hydrogen atoms are performed using a combination of quantum chemical calculations, Fourier-transform infrared, and solid-state NMR spectroscopy. Eu2+ doped samples exhibit cyan emission (λmax=498nm, fwhm=50nm/1981cm-1) when excited with ultraviolet light with an impressive internal quantum efficiency (IQE) of 41%, which represents the first benchmark for imidonitridophosphates and is promising for potential industrial application of this compound class.