© 2022 Elsevier B.V.Ionic gold species display remarkable features in chemical and biological activities. However, high amount of gold ions, especially Au3+ ions (200 µM), seriously threaten living organisms and vital human organs. Therefore, accurate detection of Au3+ ions is highly desirable. In this work, a novel rhodamine based optical and electrochemical active probe, integrated with triphenylamine and thiophene moiety, exhibited highly selective detection of Au(III) ions compared to the other metal species, such as Ag+, K+, Li+, Na+, Hg2+, Ba2+, Ca2+, Cd2+, Cu2+, Co2+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+ Pd2+, Al3+, Ce3+, Cr3+, Fe3+ and Cr6+. Exploiting hydrolysis and ring-opening reaction, the probe offers privileged properties such as naked-eye detection (colorimetric), both “turn-on” and “turn-off” fluorescence responses, voltammetric read-out with an anodic shift, low detection limit (340 and 315 nM for “turn-on” and “turn-off”, respectively), rapid response, and applicability in determining Au(III) in complex water samples.