The underpotential deposition (UPD) of copper on a Pt(111) electrode and the influence of gas coadsorbates, i.e. CO and CO2, on the thus deposited copper layer were studied in a 0.1 M HClO4 electrolyte by means of EC-STM. By UPD, an atomically flat Cu layer is formed, which exhibits a pseudomorphic (1 × 1) structure. However, it contains several point defects due to which its total coverage is less than a monolayer, in agreement with the measured charge density in the CV curves. Upon exposure to a CO-saturated solution the pseudomorphic structure collapses to a coalescent structure with many vacancy islands. This phase transition is induced by the preferential binding of CO to the Pt(111) surface. In contrast, CO2, which binds stronger to copper, does not affect the pseudomorphic structure of the Cu layer.