Unprecedented protocol, consisting in reduction of Buckminsterfullerene with Na/K alloy and successive stirring in presence of O2, affords polyhydroxylated fullerenols which are highly water soluble, from strongly basic to medium acidic conditions. The products have been characterized by means of cross polarization magic angle spinning (CPMAS) NMR, 1H‐NMR, electron, FT‐IR, Raman and mass spectroscopies. Possible paths of reaction and the role of molecular oxygen in fullerene cage‐oxidation are discussed.