The aggregation behavior in nonpolar solvents of the octyl viologen (OV) salt with the hydrophobic anion bis(trifluoromethanesulfonyl)amide (Tf2N-) has been investigated. H-1 and F-19 NMR, ESI-MS and DFT calculations suggest that large aggregates are formed in toluene, benzene and chloroform, where the salt is highly soluble. The lifetime of the aggregates is long enough to be detected as independent species by H-1 and F-19 NMR spectroscopy, together with the smaller neutral OV(Tf2N)(2) cluster. This behavior is quite at variance with usual NMR detected equilibria where only average signals are generally observed. Large aggregates are also observed in ESI-MS spectra of toluene and chloroform solutions despite the well-known low-coordinating ability of Tf2N2. It is suggested that the structure of the large aggregates mimics the thermotropic smectic phase that this system exhibits near room temperature.