Aryl radicals generated in the aqueous phase of biphasic mixtures have—regardless of a comparably low polarity— a strong preference to react with aromatic substrates in the aqueous phase and not to undergo phase-transfer into a lipophilic phase, independent from the presence of a surfactant. These results represent an important prerequisite toward future studies in biological systems, which typically consist of various compartments of either hydrophilic or lipophilic character.