Controlled electrodeposition and surface nanostructuring are very promising approaches to tailor the structure of the electrocatalyst surface, with the aim to enhance their efficiency for sustainable energy conversion reactions. In this highlight, we first summarise different strategies to modify the structure of the electrode surface at the atomic and sub-monolayer level for applications in electrocatalysis. We discuss aspects such as structure sensitivity and electronic and geometric effects in electrocatalysis. Nanostructured surfaces are finally introduced as more scalable electrocatalysts, where morphology, cluster size, shape and distribution play an essential role and can be finely tuned. Controlled electrochemical deposition and selective engineering of the surface structure are key to design more active, selective and stable electrocatalysts towards a decarbonised energy scheme.