The production of high-purity hydrogen for primary energy generation is a key goal in the renewable energy consumption model. Currently, hydrogen production through electrolysis remains quite expensive, making the development of new non-noble metal catalysts for the cathodes of acidic electrolyzers a promising strategy to lower the costs associated with this technology. In this work, Cu, Zn and Zn/Cu particles in the absence and the presence of 1,3,5-benzenetricarboxylic acid (BTC) have been synthesized via binder-free electrodeposition onto an indium tin oxide (ITO) surface as electrocatalysts to improve the hydrogen evolution reaction (HER) in acidic media. Main results highlight the fundamental role of the metal-organic framework (i.e., BTC), combined with the synergistic effect of both metal elements (i.e., Zn and Cu), in creating a uniform deposition of small crystalline particles on the ITO surface. Consequently, a low-cost and robust electrocatalyst (Zn/Cu-BTC/ITO) with enhanced catalytic performance toward the HER was synthesized. Finally, this work emphasizes how electrochemically modified surfaces, created using low-cost metals and straightforward sustainable synthesis methods, can generate atomically dispersed active sites that enhance both electrocatalytic activity and stability. This approach could contribute to the development of innovative electrodes, improving performance while reducing the cost of electrolyzers.