Metal–thiolate complexes have been the focus of research for several years because of their unique photophysical properties and their use as a precursor for synthesizing various well-defined metal nanoclusters. A rational understanding of their structure–property relationship is necessary to realize their full potential in practical applications. Herein, we demonstrate the synthesis of a unique copper–thiolate complex with reversibly switchable catalytic and photoluminescence (PL) properties. The as-synthesized complex at basic pH (Complex B) showed cyan PL with a strong peak at ∼488 nm (cyan) and a small shoulder peak at ∼528 nm (green). When the pH of the complex was changed to acidic (Complex A), the PL was switched to light green. Such pH-responsive PL properties were demonstrated to be useful for pH and CO₂ sensing. The switchable properties originate from their two distinct structural states at two different pHs. We found that Complex A was resistant to high concentrations of a strong reducing agent, and had an intermediate oxidation state of copper (Cu⁺) with good thermodynamic stability. Furthermore, the switchable catalytic property was investigated with a 4-nitrophenol reduction and 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation reaction. The reduction kinetics followed pseudo-first-order, where the catalytic activity was enhanced by more than 10³ times when Complex B was switched to Complex A. A similar trend was also observed for TMB oxidation. Our design strategy demonstrates that redox switchable metal–thiolate complexes could be a powerful candidate for a plethora of applications.