Melamium bromide and melamium iodide were synthesized from dicyandiamide in the presence of ammonium halides in evacuated Duran glass ampoules at temperatures of 450 °C. The crystal structures of both compounds were obtained from single‐crystal X‐ray diffraction. Melamium bromide C6N11H10Br crystallizes in space group P21/n [no. 14, a = 7.0500(5), b = 28.7096(18), c = 10.8783(8) Å, β = 96.060(2)°, Z = 8, wR2 = 0.2231] and exhibits a layer‐like arrangement of melamium ions, wherein both planar as well as twisted molecular structures of the cations occur. Melamium iodide C6N11H10I crystallizes in space group P21/c [no. 14, a = 6.8569(3), b = 11.9949(6), c = 14.0932(6) Å, β = 97.613(2)°, Z = 4, wR2 = 0.0654], however in a structure completely different from the one of melamium bromide. The melamium iodide structure is comprised of stacks of planar melamium ions that form complex, hydrogen‐bonded network layers with iodide ions within the layers. Both compounds were further characterized by FTIR spectroscopy, mass spectrometry, and elemental analyses. Melamium bromide and melamium iodide could be obtained as air stable and colorless crystals. Samples are crystallographically phase pure as shown by Rietveld refinement.