Stability constants of complexes formed by gossypol and by ten of its Schiff bases with Ag+ cations were determined by the potentiometric method. The potentiometric and ESI MS experiments indicate the formation of AgL+ and Ag2L2+ complexes between the Schiff bases G1-G7 and Ag+ cations as well as the formation of AgL+, Ag2L2+, AgL2+ and Ag3L23+ complexes between the Schiff bases G8-G10 and Ag+ cations. The highest stability constant was found for the AgL+ complex of G8 Schiff base and the lowest one for the AgL+ complex of G molecule. The C-13 NMR spectra of mixtures between G and AgClO4 as well as G1-G10 and AgClO4 indicate that the complexation of the Ag+ cations is exclusively realized by the aldehyde-aldehyde tautomer of gossypol and by the enamine-enamine form of gossypol Schiff bases, respectively. We show that the main coordination sites for the Ag+ metal cations are either the oxygen or the nitrogen atoms of the amine parts of the Schiff bases of gossypol. The energetically most favorable structures of the Ag+ complexes with gossypol (G) or with the gossypol Schiff bases (G1-G10) were calculated and visualized by the AM1d method at an semiempirical level of theory.