A novel and enhanced electrosynthesis protocol that allows the deposition of thin films of Co/Al and Co/Fe layered double hydroxides (LDHs) on different supports is hereby proposed. The approach is based on potentiodynamic cathodic reduction. All the films have been characterised by cyclic voltammetry, powder X-ray diffraction, scanning electron microscopy, and Raman and atomic emission spectroscopies. Moreover, LDHs electrosynthesised on carbonaceous materials have also been investigated by X-ray absorption spectroscopy to analyse their local metal structure. These substrates are particularly interesting for the plethora of LDH applications ranging from energy storage, sensing, and electrocatalysis, and are also of industrial importance, due to their low cost, ecocompatibility, and easy handling. In particular, the material was exploited for 5-(hydroxymethyl)furfural (HMF) electro-oxidation.