Although the Cu2+‐sorbitol complex [Cu2+‐Sorb] structure in crystalline state has been determined by X rays, it is not known in solution, where most studies of this complex are performed. Therefore, the goal of this work was to obtain information about the structure of this complex in aqueous solution using nuclear magnetic resonance and electron paramagnetic resonance spectroscopies. The magnetic resonance results indicate that the complex is formed at approximately pH 12. In this pH the sorbitol 1H relaxation times were so short (broad line) that was not possible to use standard nuclear magnetic resonance parameters (nuclear Overhauser effect and spin–spin coupling constants values) to solve the three‐dimensional structure. However, valuable structural information about the complex in solution was obtained. The relaxation results indicate that the Cu2+ ions are buried in the structure and not accessible to solvent; the 1H and 13C spectra shows strong paramagnetic shift effect indicating short distance between these nuclei and Cu2+ in the structure. No electron paramagnetic resonance signal was observed in pH 12 indicating strong Cu2+‐ Cu2+ dipolar interaction, compatible to Cu2+‐Cu2+ distances measured in crystal, from 1.148 to 1.393 Angstroms. The complex self‐diffusion coefficient (D) of 1.58 × 10−10 m2/s value, determined by Diffusion‐Ordered Spectroscopy, is compatible to a molecular weight of 3–6 KDa. Therefore, these results corroborate that the [Cu2+‐Sorb] complex is assembled in solution, at pH 12, with several structural parameters compatible to the toroidal hexadecacuprate supramolecular structure determined in solid state.