The paper reports an unprecedented spectrophotometric determination of amines in chloroform, in which amines are not transformed into colored derivatives. This result has been achieved by exploiting the acid base properties of the tight-ion paired metal complexes [(HR2DTO)Pt(H2R2DTO)][Cl], which are able to donate a HCl molecule to an amine, giving rise to an ammonium salt and to the neutral complexes [(HR2DTO)(2)Pt]. The circumstance that [(HR2DTO)Pt(H2R2DTO)] [Cl] and [(HR2DTO)(2)Pt] species show different absorptions in the visible region of the electromagnetic spectrum enables the aforementioned platinum complexes to behave as self-indicating titrants in the spectrophotometric determination of aliphatic amines, which are known to be UV-vis transparent. The new method has been tested by determining a series of fatty amines in the bulk and gave excellent results. The limits of applicability of this method (pK(a) > 4) were found by testing a series of benzodiazepines.