The preparation of crystalline [NBu4] [AuCl2] in 85-90% yield by the reduction of [NBu4] [AuCl4] with sodium acetylacetonate is reported together with procedures for the quantitative synthesis of crystalline [NBu4] [AuX4] (X = Cl, Br) through direct oxidation of metallic gold in X2/[NBu4] X/ethanol, and the determination of the crystal structure of [NBu4] [AuCl4].