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Carbonium ions are an important class of reaction intermediates, but their dynamic evolution is difficult to be monitored by in situ techniques under experimental conditions because of their extremely short lifetime. Probably the most famous case is 2‐norbornyl cation (2NB⁺): its existing form (classical or non‐classical) had been debated for decades, until the concrete proof of non‐classical geometry was achieved by X‐ray crystallographic characterization at ultra‐low temperature (40 K) and super acidic environment. However, we lack the understanding about 2NB⁺at ambient conditions. Herein, by taking advantage of the confinement effect and delocalized acidic environment of zeolites, we successfully stabilized 2NB⁺and unequivocally confirmed its “non‐classical” structure inside the ZSM‐5 zeolite byab initiomolecular dynamics simulations and¹³C solid‐state nuclear magnetic resonance experiments. It is the first time to in situ observe the non‐classical 2NB⁺without the super acidic environment at ambient temperature, which provides a new strategy to expand the carbocation chemistry.

Carbonium ions are an important class of reaction intermediates, but their dynamic evolution is difficult to be monitored by in situ techniques under experimental conditions because of their extremely short lifetime. Probably the most famous case is 2‐norbornyl cation (2NB⁺): its existing form (classical or non‐classical) had been debated for decades, until the concrete proof of non‐classical geometry was achieved by X‐ray crystallographic characterization at ultra‐low temperature (40 K) and super acidic environment. However, we lack the understanding about 2NB⁺at ambient conditions. Herein, by taking advantage of the confinement effect and delocalized acidic environment of zeolites, we successfully stabilized 2NB⁺and unequivocally confirmed its “non‐classical” structure inside the ZSM‐5 zeolite byab initiomolecular dynamics simulations and¹³C solid‐state nuclear magnetic resonance experiments. It is the first time to in situ observe the non‐classical 2NB⁺without the super acidic environment at ambient temperature, which provides a new strategy to expand the carbocation chemistry.