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By nucleophilic addition of phosphite P(OMe) 3 to a cage‐opened C 60 derivative, α‐hydrophosphate and enol phosphate were obtained as kinetic and thermodynamic products, respectively. Different from classical Abramov products bearing a phosphorus–carbon bond, these products have a phosphorus–oxygen bond. The observed anomaly originates from the fully conjugated π‐system which significantly stabilizes zwitterionic intermediates bearing a phosphorus–oxygen bond. The thus formed enol phosphate was found to exhibit an intense absorption band that extended to 730 nm, reflecting the intramolecular charge transfer transitions. We also report domino phosphorylation reactions which gave a cage‐opened C 60 derivative bearing a direct P–C bond.