The construction of nanostructured materials for their application in electrochemical processes, e.g., energy storage and conversion, or sensing, has undergone a spectacular development over the last decades as a consequence of their unique properties in comparison to those of their bulk counterparts, e.g., large surface area and facilitated charge/mass transport pathways. This has driven strong research on the optimization of nanostructured materials for the fabrication of electrochemical devices, which demands techniques allowing the assembly of hybrid materials with well-controlled structures and properties. The Layer-by-Layer (LbL) method is well suited for fulfilling the requirements associated with the fabrication of devices for electrochemical applications, enabling the fabrication of nanomaterials with tunable properties that can be exploited as candidates for their application in fuel cells, batteries, electrochromic devices, solar cells, and sensors. This review provides an updated discussion of some of the most recent advances on the application of the LbL method for the fabrication of nanomaterials that can be exploited in the design of novel electrochemical devices.