Endohedral metallofullerenes (EMFs) containing lanthanides have been intensively studied in recent years. By contrast, actinide endohedral fullerenes remain largely unexplored. Herein, for the first time, we report the single crystal structure and full characterization of an actinide endohedral fullerene, Th@C-82, which exhibits remarkably different electronic and spectroscopic properties compared to those of lanthanide EMFs. Single crystal X-ray crystallography unambiguously established the molecular structure as Th@C-3v(8)-C-82. Combined experimental and theoretical studies reveal that Th@C-3v(8)-C-82 is the first example of an isolated monometallofullerene with four electrons transferred from the metal to the cage, with a surprisingly large electrochemical band gap of 1.51 eV. Moreover, Th@C-3v(8)-C-82 displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.