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This work presents a comprehensive study of the UV–Visible and fluorescence properties, as well as the redox behavior of the [AuIII(Salen)]Cl complex in acetonitrile. The [AuIII(Salen)]+ complex exhibited intriguing fluorescence and phosphorescence characteristics on an indium tin oxide (ITO)-coated glass plate when excited at wavelength λexc ~ 260 nm, with fluorescence emission observed at λems ~ 437 nm and phosphorescence at λems ~ 520 nm. The origin of fluorescence emission was attributed to the intra-ligand charge transfer effect, commonly known as the "Push–Pull" effect. The electrochemical behavior of [AuIII(Salen)]+ on a glassy carbon electrode (GCE) revealed a remarkable one-step three-electron reduction process, leading to the reduction of [AuIII(Salen)]+ to Au(0). Furthermore, the reduction of [AuI(Salen)]− to Au(0) resulted in the removal of gold metal from the SalenH2 ligand. The electrochemical results suggested a mixed diffusion-adsorption redox process occurring at the GCE surface, indicating the involvement of both diffusion and adsorption during redox reactions. The cyclic voltammogram demonstrated the non-reversibility of the electrochemical redox reactions. Overall, the redox behavior of the [AuIII(Salen)]Cl complex proved to be intriguing, opening up avenues for further exploration and potential applications of this complex in various fields. [ABSTRACT FROM AUTHOR]