Three examples of the electrochemical deposition of intermetallic phases are shown. Electrodeposition of the single-phase β′-brass superlattice at underpotentials of Zn in Cu-Zn alloy plating is explained by an accumulative underpotential deposition (UPD) mechanism. Growth of the Cu-Sn intermetallic phase layer in the contact immersion deposition of Sn onto Cu is accounted for by a UPD/vertical solid-state diffusion mechanism. Ag3Sn formation in the Sn/Ag-nanoparticle composite plating is illustrated by atomic site exchange at the interface between the deposited Sn matrix and the occluded Ag nanoparticles.