Ammine copper(I) cyanamide, Cu4(NCN)2NH3, was obtained as a white powder from the reaction between CuCl and H2NCN in concentrated ammonia solution. X‐ray and neutron diffraction experiments yield the hexagonal system with space group P63mc (no. 186) and a = 5.7661(1) Å, c = 10.7817(3) Å, and Z = 2. The structure is characterized by layers of monovalent copper ions with an average Cu–Cu distance of 2.89Å, and the layers are connected through two crystallographically independent NCN2− units. While one CuI is linearly bonded to an NCN2− unit and an additional NH3 molecule, the other CuI is also linearly coordinated but by two NCN2− groups; the Cu–N bonds lie between 1.86–1.98Å. The C–N bond lengths and angles evidence both NCN2− groups as essentially linear cyanamides.