It is desirable and challenging to prevent E-resveratrol (E-RSV) from photoisomerizing to its Z-configuration to preserve its biological and pharmacological activities. The aim of this research was to evaluate the photostability of E-RSV-loaded supramolecular structures and the skin penetration profile of chemically and physically stable nanoestructured formulations. Different supramolecular structures were developed to act as carriers for E-RSV, that is, liposomes, polymeric lipid-core nanocapsules and nanospheres and solid lipid nanoparticles. The degrees of photostability of these formulations were compared with that of an ethanolic solution of E-RSV. The skin penetration profiles of the stable formulations were obtained using vertical diffusion cells (protected from light and under UVA radiation) with porcine skin as the membrane, followed by tape stripping and separation of the viable epidermis and dermis in a heated water bath. Photoisomerization was significantly delayed by the association of resveratrol with the nanocarriers independently of the supramolecular structure. Liposomes were the particles capable of maintaining E-RSV concentration for the longest time. On the other hand, E-RSV-loaded liposomes reduced in size showing low physical stability under UVA radiation. In the dark, the skin penetration profiles were very similar, but under UVA radiation the E-RSV-loaded nanocarriers showed increasing amounts in the total epidermis.