The 1:1 molar reaction of WCl6 with tribenzylamine (tba), in dichloromethane, selectively afforded the iminium salt [(PhCH2)2N═CHPh][WCl6], 1, and the ammonium one [tbaH][WCl6], 2, in equimolar amounts. The products were fully characterized by means of spectroscopic methods, analytical methods, and X-ray diffractometry. Density functional theory calculations were carried out with the aim of comprehending the mechanistic aspects.