Multiphase chemical systems are greatly different than bulk solutions, as they provide a unique environment for reactions to proceed and have unique physicochemical properties. Thus, new tools need to be developed to gain a more detailed understanding of these systems. Here, we use electrogenerated chemiluminescence (ECL) to elucidate phase boundaries precisely and comprehensively between aqueous droplets and an organic continuous phase owing to ECL's unprecedented spatial resolution (a few micrometers) confined at the electrode surface. Phase-resolved mapping was accomplished by selecting a luminophore that is soluble in both phases while selecting two coreactants that are exclusively soluble in one phase or the other. This type of system allows us to map the complex liquid|electrode and the liquid|liquid interfaces in a multiphase system. We show that electrical connectivity is not conserved throughout solvent inclusions, which result from neighboring droplet coalescence, indicating an unexpected initial lack of electronic communication. These results have great importance to energy storage and conversion devices and wearable/implantable sensors, which are dominated by complex, multiphase environments.