Low melting point eutectic systems, such as the eutectic gallium-indium (EGaIn) alloy, offer great potential in the domain of nanometallurgy; however, many of their interfacial behaviors remain to be explored. Here, a compositional change of EGaIn nanoalloys triggered by polydopamine (PDA) coating is demonstrated. Incorporating PDA on the surface of EGaIn nanoalloys renders core-shell nanostructures that accompany Ga-In phase separation within the nanoalloys. The PDA shell keeps depleting the Ga3+ from the EGaIn nanoalloys when the synthesis proceeds, leading to a Ga3+-coordinated PDA coating and a smaller nanoalloy. During this process, the eutectic nanoalloys turn into non-eutectic systems that ultimately result in the solidification of In when Ga is fully depleted. The reaction of Ga3+-coordinated PDA-coated nanoalloys with nitrogen dioxide gas is presented as an example for demonstrating the functionality of such hybrid composites. The concept of phase-separating systems, with polymeric reservoirs, may lead to tailored materials and can be explored on a variety of post-transition metals.