In this work, we have developed a molecule (BT-DCAF) for hydrogen production based on two caffeine units covalently linked to a benzothiadiazole center (Figure ). For comparison, a mono-substituted benzothiadiazole (BT-MCAF) with one caffeine unit has been also synthesized. BT-DCAF shows reversible access to three reduction states. Furthermore, BT-DCAF can form an imidazoline-based hydride species through electrochemical reduction in the presence of strong organic acids. This active species functions as a highly stable molecular electrocatalyst towards H2 evolution at mild potentials in DMSO.