Molecular self-assembly primarily occurs in solution. To better understand this process, techniques capable of probing the solvated state are consequently required. Small-angle scattering (SAS) has a proven ability to detect and characterise solutions, but is rarely applied to more complex assembly shapes. Here, we apply small-angle X-ray and neutron scattering to observe toroidal assemblies in solution. Combined analysis confirms that the toroids have a core-shell structure, with a π-conjugated core and an alkyl shell into which solvent penetrates. The dimensions determined by SAS agree well with those obtained by (dried-state) atomic force microscopy. Increasing the number of naphthalene units in the molecular building block yields greater rigidity, as evidenced by a larger toroid and a reduction in solvent penetration into the shell. The detailed structural analysis demonstrates the applicability of SAS to monitor complex solution-based self-assembly.Self-assembly processes range from the micellisation of amphiphiles [1][2][3] to supramolecular polymerization [4] and onwards to the more elaborate folding of DNA origami.[5] When apolar molecules associate, solvent-solvent and solvent-solute interactions play a key role in the assembly process.[6] Upon solvent removal, the assembly structure is rarely unaffected, necessitating the probing of the sample structure in solution in order to form an accurate assembly model. Unfortunately, this is often difficult to do, and, while cryo-electron microscopy can reveal high-resolution structures in (frozen) solution, [1,7] there are only a few reports of its use in non-aqueous solutions.[2]Conversely, small-angle scattering (SAS) techniques using Xrays (SAXS) [8] or neutrons (SANS) [9] can detect molecular assemblies with dimensions typically between 1-100 nm in solution. SAS results offer a bulk average over an appreciable volume, are dominated by the most commonly existing assembly structure, and therefore have a high statistical relevancy. SAXS and SANS are routinely used to probe various supramolecular assemblies, including molecular capsules and tubes, [10,11] micelles, [2,3,12,13] vesicles, [14,15] organogels, [2,16] and protein tertiary structures.[17] Combining SAXS and SANS can be particularly insightful. The SAXS signal arises from regions contrasting in electron density, while SANS (in this case) highlights 1 H-rich regions of an assembly dispersed in a 2 D-rich solvent.[9]Therefore, for molecules comprising both π-conjugated (e − -rich, 1 H-poor) and aliphatic ( 1 H-rich, e − -poor) parts such as asphaltenes [18] or alkyl-fullerene derivatives, [2] the SAXS and SANS signals will derive from the π-conjugated-rich and aliphatic-rich parts of an assembly, respectively. In these cases, combined SAXS and SANS allows the detection not only of a particular assembly morphology in solution but also of the internal structure. In this regard, the unique self-assembly of 1 in apolar media is an attractive target for SAS investigations ( Figure 1a). Molecule 1, ...