A reactive radical species, nitric oxide (NO), was encapsulated in a unimolecular form inside an open‐cage fullerene derivative under high‐pressure conditions in the solid state. Surprisingly, the molecular complex showed sharp 1H NMR signals despite the existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the escape rate of the NO was determined experimentally. After constructing a stopper on the rim of the opening, the NO was found to stay inside the cage even at 50 °C. The ESR measurements of the powdery sample showed paramagnetic properties at low temperature. The single‐crystal X‐ray structure analysis clearly demonstrated the existence of the encapsulated NO molecule, suggesting rapid rotation inside the cage. The 1H NMR chemical shifts displayed a large temperature dependence owing to the paramagnetic effects.