The environment-dependent behavior of invertible polyesters has been studied by H-1 NMR spectroscopy. In dilute toluene solutions, the micelle exterior is made up of the lipophilic fragments, and the interior consists of the hydrophilic constituents. The polyester inverts the structure in an aqueous medium to form micelles with a hydrophobic inner part and a hydrophilic outer part. Increasing polyester concentration leads to the formation of hierarchical structures both in toluene and in an aqueous medium as a result of the aggregation of unimolecular micelles and the formation of hydrophilic and lipophilic domains. On the contrary, no unimolecular micelles or micellar aggregation has been observed in acetone or chloroform.