AbstractEnzymes, especially some metalloenzymes, are exceptional catalysts for redox reactions with technological applications in several fields, including energy conversion systems and producing fuels and value‐added chemicals. Because of that, they have inspired the development of synthetic catalysts to obtain high‐performance materials. However, several fundamental aspects should be better understood to achieve this goal, such as enzyme catalysis and the role of the three‐dimensional catalytic site. Therefore, this review addresses key structural and activity aspects of some remarkable metalloenzymes and discusses three‐dimensional catalysis as an approach to enzyme catalysis. Also, the case of the multicopper oxidase enzymes is shown as an example of how the three‐dimensional coordination environment of the copper ions in the active site can impact catalysis.