Gold compounds engage an important place in the field of medicinal chemistry due to their therapeutic properties. Since the last four decades, Au(I) and Au(III) complexes have attracted the attention of researchers due to their anti-tumor proprieties and the different mechanisms of action they display in comparison to conventional anticancer platinum compounds. Au(I/III) complexes can inhibit the activity of enzymes containing thiols including thioredoxin reductase; nevertheless, the affinity for several therapeutic targets has been confirmed in recent years. The properties conferred by auxiliary ligands such as phosphines (PR3) and N-heterocyclic carbenes (NHCs) to gold complexes have been key to the development of more promising anticancer compounds. In the same way, it has happened with the inclusion of some multidentate ligands in Au(III) complexes, increasing their stability and selectivity for tumor cells. In this review, we discuss the anticancer effects of Au(I) complexes containing PR3 and NHCs ligands as well as Au(III) complexes containing multidentate ligands especially those that have high cytotoxicity and information on the mechanism of action, as well as attempts to target identification and validation.