It is shown that dipolar solid state 15N NMR spectroscopy can be employed in order to estimate the positions of hydrogen bond deuterons in polycrystalline 15N labeled proton sponges containing an intramolecular N…H…N hydrogen bond. For singly 15N labeled 1, 8‐bis(dimethylamino)naphtalene. LPF6 (1‐h: LH, 1‐d: LD), an asymmetric hydrogen bond with cubic average distances between the two nitrogen atoms and the hydrogen bond deuteron of 1.19 Å and 1.47 Å are obtained. These values are in accordance with the N…H distances of 1.19(7) Å and 1.43(6) Å, obtained previously by x‐ray diffraction at 150 K.