We report the synthesis, ESR spectroscopic and spin coherent properties of the dimetallofullerene Sc2@C80(CH2Ph). The single-electron metal–metal bond of the Sc2 dimer inside the fullerene's cage is stabilized with the electron spin density being fully localized at the metal bond. This results in an extraordinary strong hyperfine interaction of the electron spin with the 45Sc nuclear spins with a coupling constant a = 18.2 mT (∼510 MHz) and yields a fully resolved hyperfine-split ESR spectrum comprising 64 lines. The splitting is present even at low temperatures where the molecular dynamics are completely frozen. The large extent and the robustness of the hyperfine-split spectra enable us to identify and control the well-defined transitions between specific electron-nuclear quantum states. This made it possible to demonstrate in our pulse ESR study the remarkable spin coherent dynamics of Sc2@C80(CH2Ph), such as the generation of arbitrary superpositions of the spin states in a nutation experiment and the spin dephasing times above 10 μs at temperatures T < 80 K reaching the value of 17 μs at T ≤ 20 K. These observations suggest Sc2@C80(CH2Ph) as an interesting qubit candidate and motivate further synthetic efforts to obtain fullerene-based systems with superior spin properties.