A method is presented to obtain solvent-independent redox potential systems using solid-state electrochemistry of alkynyl−diphosphine dinuclear Au(I) complexes (AuC 2 R) 2 PPh 2 C 6 H 4 PPh 2 (L1, R = Fc; L2, R = C 6 H 4 Fc) containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes based on ferrocenyl-centered oxidation processes involving anion insertion. Midpeak potentials appear to be essentially solvent-independent upon referring it to the bis(η-biphenyl)chromium(I)/bis(biphenyl)chromium(0) couple. Theoretical modeling of diffusion processes allows us to combine voltammetric and chronoamperometric data to determine equilibrium potentials that are strictly solvent-independent. Data for water, MeOH, EtOH, MeCN, DMS, DMF, and NM are provided.