A new perchlorate salt of melem (2,6,10-triamino-s-heptazine, C6N7(NH2)3) was obtained from an aqueous solution of HClO4 at lower concentration than the ones reported for the synthesis of melemium perchlorate monohydrate (HC6N7(NH2)3)ClO4·H2O. The new salt was identified as melemium melem perchlorate (HC6N7(NH2)3)ClO4·C6N7(NH2)3 representing a melem adduct of water free melemium perchlorate. The crystal structure was solved by single-crystal X-ray methods (, no. 2, Z = 2, a = 892.1(2), b = 992.7(2), c = 1201.5(2) pm, α = 112.30(3), β = 96.96(3), γ = 95.38(3)°, V = 965.8(4)·106 pm3, 4340 data, 387 parameters, R1 = 0.039). Melemium melem perchlorate crystallizes in a layer-like structure containing both protonated HC6N7(NH2)3 and non protonated C6N7(NH2)3 moieties in the coplanar layers as well as perchlorate ions between them, all of which being interconnected by hydrogen bonds. Vibrational spectroscopic investigations (FTIR and Raman) of the salt were conducted.