One probe for testing whether or not the 2-norbornyl cation is non-classical is investigating the inherent symmetry of the cation. Many spectroscopic tools, such as nuclear magnetic resonance spectroscopy (NMR spectroscopy) and Raman spectroscopy, give hints about the reflectional and rotational symmetry present in a molecule or ion. Each of the three proposed structures of the 2-norbornyl cation illustrates a different molecular symmetry. The non-classical form contains a reflection plane through carbons 4, 5, 6, and the midpoint of carbons 1 and 2. The classical form contains neither reflectional nor rotational symmetry. The protonated nortricyclene structure contains a C-symmetric rotation axis through carbon 4.
Each peak in an NMR spectrum corresponds to a set of a particular element's atoms that are in similar chemical environments. The NMR spectrum of the antimony chloropentafluoride salt of the 2-norbornyl cation is not helpful at room temperature because hydride shifts occur faster than the timescale of an NMR experiment; most of the hydrogens are thus seen as equivalent and are accounted for in the same absorption peak. By lowering the temperature of the NMR experiment to &minus;60 °C, hydride shifts are "frozen out" and more structural information can be gleaned from the spectrum. Researchers found that at these low temperatures, the H NMR spectrum matched what would be expected for the non-classical structure of the ion.
H and C NMR studies were able to confirm that any proposed Wagner-Meerwein rearrangements occurred faster than the timescale of the NMR experiment, even at low temperatures. For molecules in static equilibrium with respect to rearrangements, NMR reveals how many sets of symmetry-related nuclei are in the molecule and how many nuclei each of these sets accounts for via spectrum integration. For molecules in dynamic equilibrium such as the 2-norbornyl cation, nuclei within each set can also be transformed to one another through rearrangements with fast reaction rates. Since the proposed dynamic equilibrium of the classical ion proponents had very fast rates of rearrangement, the first NMR studies did not favor nor invalidate any of the three proposed structures. But by using solid-state NMR analysis, one can lower the temperature of the NMR experiment to  and thus significantly slow down any rearrangement phenomena. Solid-state C NMR spectra of the 2-norbornyl cation shows that carbons 1 and 2 are in identical chemical environments, which is consistent only with the non-classical picture of the 2-norbornyl cation.
Raman spectra of the 2-norbornyl cation show a more symmetric species than would be expected for a pair of rapidly equilibrating classical ions. Since the proposed reaction rates for the classical ion rearrangements are slower than the Raman timescale, one would expect the Raman spectra to indicate a less symmetric species if the classical picture were correct.
Some studies of the C NMR in particular favored interpretation via the protonated nortricyclene structure. In addition, Raman spectra of the 2-norbornyl cation in some acidic solvents show an absorption band at 3110 cm indicative of an electron-depleted cyclopropane ring. Since that absorption band would be expected in the C-symmetric protonated nortricyclene, some scientists claimed this as convincing evidence for this interpretation. Other chemists have postulated that the properties of the 2-norbornyl cation are very dependent on the solvent environment. Though the high acidity and low nucleophilicity of the solvents used in aforementioned experiments may cause the protonated nortricylconium geometry to be the most stable, this geometry need not be the most energetically favorable in other solvents.