The organic diammonium salt N,N′-dibenzyl-N,N,N′,N′-tetramethylethylenediammonium dibromide dihydrate, (dbtmen)Br₂.2H₂O (1), was prepared by the reaction of N,N,N′,N′-tetramethyl-ethylenediamine (tmen) with benzyl bromide.1 crystallizes in the triclinic space group$$P\bar 1$$ with the following unit cell dimensions for C₂₀H₃₄Br₂N₂O₂ (M = 494.31):a = 8.6672(6) Å,b = 11.7046(8) Å,c = 11.7731(8) Å, α = 76.988(8)°, β = 88.978(8)°, γ= 76.198(8)γ,V= 1129.26(13) ų, Z=2. Three components, namely the (dbtmen)²⁺ dication, two bromide anions and two crystal water molecules constitute the structural arrangement of1. H₂O molecules are linked to bromide anions via O-H...Br hydrogen bonding interactions resulting in the formation of a four-membered O₂Br₂ cyclic dibromide. The O₂Br₂ units and the dications are arranged as alternating layers extending in the crystallographicbc plane. The arrangement of anions and cations may be viewed as a typical lamellar structure. The crystal water molecules can be removed by heating 1 at 140°C and the anhydrous dibromide thus formed can be fully rehydrated as evidenced by IR spectra and X-ray powder patterns.