Nanosized particles of liquid metals are emerging materials which hold promise for applications spanning from microelectronics to catalysis. Yet, the knowledge of their chemical reactivity is largely unknown. Here, we study the reactivity of liquid Ga and Cu nanoparticles under the application of a cathodic voltage. We discover that the applied voltage and the spatial proximity of these two particle precursors dictate the reaction outcome. In particular, we find that a gradual voltage ramp is crucial to reduce the native oxide skin of the gallium and enable reactive wetting between the Ga and the Cu nanoparticles; instead, a voltage step causes dewetting between the two. We determine that the use of liquid Ga/Cu nanodimer precursors, which consist of an oxide-covered Ga domain interfaced with a metallic Cu domain, provide a more uniform mixing and result in more homogeneous reaction products compared to a physical mixture of Ga and Cu NPs. Having learned this, we obtain CuGa2 alloys or solid@liquid CuGa2@Ga core@shell nanoparticles by tuning the stoichiometry of the Ga and Cu in the nanodimer precursors. These products reveal an interesting complementarity of thermal and voltage driven synthesis to expand the compositional range of bimetallic NPs. Finally, we extend the voltage-driven synthesis to the combination of Ga with other elements (Ag, Sn, Co, W). By rationalizing the impact of the native skin reduction rate, the wetting properties and the chemical reactivity between Ga and other metals on the results of such voltage-driven chemical manipulation, we define the criteria to predict the outcome of this reaction and set the ground for future studies targeting various applications for multielement nanomaterials based on liquid Ga.