The Electrochemical Atomic Layer Deposition (E-ALD) technique is used for the deposition of ultrathin film of bismuth (Bi) compounds. Exploiting the E-ALD it was possible to obtain high controlled nanostructured depositions as needed for the application of these materials for novel electronics (topological insulators) and opto-electronics applications. Electrochemical studies have been conducted to determine the Underpotential Deposition (UPD) of Bi on selenium (Se) to obtain the Bi₂Se₃ compound on the Ag (111) electrode. Verifying the composition with the X-ray Photoelectron Spectroscopy (XPS) emerged that, after the first monolayer, the deposition of Se is stopped. Thicker deposits were synthesized exploiting a time-controlled deposition of massive Se. Then we move to discover the optimal conditions to deposit a single monolayer of metallic Bi directly on Ag.