The interplay between adsorption, underpotential deposition and excess bond enthalpy in the deposition of alloys and intermetallic will be discussed based on selections from recent work. Examples of limiting behavior will be presented that range from the deposition of solid-solutions, e.g. Pt-Cu and Pt-Fe group alloys, to intermetallics, e.g. Pt-Pb, to immiscible, e.g. Cu-Pb, systems. In addition, the impact of “parasitic” reactions, such as electrolyte breakdown, on the deposition of elements and alloys will be briefly discussed. The utility of a close coupling between electroanalytical, gravimetric, metallurgical and surface science measurements to reveal the underlying thermodynamic and kinetic influences on co-deposition process will be highlighted.