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Hyperbranched and star shaped polymers have raised tremendous interest because of their unusual structural and photochemical properties, which provide them potent applications in various domains, namely in the biomedical field. In this context, the development of adequate tools aiming to probe particular three-dimensional features of such polymers is of crucial importance. In this service, ion mobility mass spectrometry was used to experimentally derive structural information related to cationized linear and star shaped poly-ε-caprolactones as a function of their charge state and chain length.