Hypothesis: Catanionic vesicles based on large-scale produced surfactants represent a promising platform for the design of innovative, effective and relatively inexpensive nano-vehicles for a variety of actives. Structural, dynamic and functional behavior of these aggregates is finely tuned by the molecular features of their components and can be opportunely tailored for their applications as drug carriers. Experiments: Here we investigate the aggregates formed by CTAC and SDS, two of the most diffused surfactants, by means of Dynamic Light Scattering, Small Angle Neutron Scattering and Electron Paramagnetic Resonance spectroscopy (EPR). The exploitation of these aggregates as nano-vehicles is explored using the poorly water-soluble antioxidant trans-resveratrol (t-RESV), testing t-RESV solubility and antioxidant activity by means of UV, fluorescence spectroscopy and EPR. Findings: The presence of a large stability region of catanionic vesicles on the CTAC-rich side of the phase diagram is highlighted and interpreted in terms of the mismatch between the lengths of the surfactant tails and of first reported effects of the chloride counterions. CTAC-SDS vesicles massively solubilize t-RESV, which in catanionic vesicles exerts a potent antioxidant and radical-scavenging activity. This behavior arises from the positioning of the active at the surface of the vesicular aggregates thus being sufficiently exposed to the external medium. (C) 2017 Elsevier Inc. All rights reserved.