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However, the fabrication of devices with different compartments usually requires the use of toxic solvents, and\/or the adaptation of technically demanding methods, including precision microfluidics and multistep processes. The spontaneous formation of multi\u2010core capsules resulting from polyelectrolyte complexation at the interface of a prototypic all\u2010aqueous two\u2010phase system is described here. The variation of polyelectrolyte concentration and complexation time are described as simple working parameters capable of driving the formation of compartments at different yields, as well as tailoring their morphology. 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