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.