Abstract The medicinal chemistry of gold has experienced an exponential development since the 2000s. For long, the mechanisms of action of gold complexes have been limited to direct coordination of the gold ion or supramolecular interactions of the whole gold complex with biomolecules. In the recent years, other modes of action of gold‐based drug candidates have emerged. Herein, we review these new modalities, including photo‐induced cytotoxicity, selective protein modification and in cellulo catalysis.