The hexameric assemblies of resorcinarenes and pyrogallolarenes are fascinating structures that can serve as nanoreactors in which new chemistry and catalysis occur. Recently, it was suggested based on SANS or SAXS that C11-resorcin[4]arene (1) forms octameric aggregates of a micellar rather than capsular structure in toluene. Here, using NMR spectroscopy, diffusion NMR, and DOSY performed on solutions of C11-resorcin[4]arene (1), C11-pyrogallol[4]arene (2), and mixtures thereof in protonated and deuterated solvents, we found that, in benzene and toluene, 1 primarily formed hexameric capsules accompanied by a minor product with diffusion characteristics consistent with an octameric assembly. In chloroform, 1 formed hexameric capsules. In toluene, 2D NMR revealed two populations of encapsulated toluene molecules in the same capsule of 1. The addition of tetrahexylammonium bromide to the assemblies of 1 in aromatic solvents drove the equilibrium toward the formation of the hexameric capsules. Interestingly, 2 formed only hexameric capsules in all solvents tested.