In summary, we have developed a small organic molecule BT-DCAF based of two covalently linked caffeine units to a benzothiadiazole core which shows electrocatalytic activity towards H2 evolution on glassy carbon electrode when combined with strong acids such as trifluoroacetic acid and phytic acid as proton sources in DMSO. We studied the relationship between molecular structure and function in regards to how symmetry and the number of covalently linked caffeine motifs affects the electrochemical reactivity and stability of two small organic molecules belonging to the benzothiadiazole class. Kinetic parameters have been determined by the means of cyclic voltammetry experiments for the electrocatalytic H2 evolution activity using BT-DCAF. A reasonable mechanism for H2 evolution involving hydride transfer is proposed based on the relevant intermediate species that were identified by combining information from cyclic voltammetry, UV-Vis spectroscopy, 1 H NMR spectroscopy, mass spectrometry experiments and DFT calculations. Long term stability, Faradaic efficiency of 92 ± 5% and TON values up to 23 ± 4 were obtained in the electrocatalytic H2 evolution at mild potentials. The development of BT-DCAF represents the molecular engineering efforts to address the current stability issues limiting the field of molecular electrocatalysis using small organic molecules for H2 evolution.