Molecular hydrogen (H2) is a fuel with high gravimetric energy density, it can be used as energy carrier by adapting existing technology and infrastructure from the natural gas industry. As compared to the traditional H2 production by steam reforming method, electrocatalytic H2 production from water splitting has attracted much interest from the research community due to the low CO2 emissions associated to the process and the possibility of using renewable electricity to power up this reaction. Conventional electrochemical production of H2 is catalyzed by metallic materials, often containing precious metals such as Pt, Pd and Ru. The inherent problems of using these elements are related to the low abundance in earth's crust and the uneven distribution of these elements across the planet. The ideal catalyst should have similar catalytic activity to that of precious metals but it should be possible to synthesize it from widely available building blocks. With this premise in mind, great interest has been raised on doped materials and small molecules based of heterocycles containing O, N, S, P and Se atoms that function as electroactive sites for fuel forming reactions. The presence of heteroatoms in small organic molecules confers them interesting (electro)chemical properties involving the storage of electrons and the ability to bind chemical entities such as H + and CO2, species of interest in fuel forming reactions such as H2 evolution and CO2 reduction. The most wellknown examples are pyridine and imidazole heterocycles that upon (electro)chemical reduction and proton binding, form species that can perform hydrogen atom (H • ) and hydride (H -) transfer, activating different substrates in the process. Although the concept is simple, most small organic molecules reported in the literature suffer from a series of issues that prevent their use as electrocatalysts. The main issues are associated to the undesired formation of radical dimers and high thermodynamic barriers for the generation of their active species by electrochemical means. In recent years, efforts to improve the performance of small organic electrocatalysts have achieved success for a handful of systems that combine biomimetic concepts with rational molecular design. For instance, catalysts based of pyridine, benzothiadiazole, bis-imidazolium-embedded heterohelicenes, benzoselenonates and phosphorus based molecules represent successful molecular electrocatalytic systems for the H2 evolution reaction.