We have studied the electronic properties of a ‘Russian-doll’-style endohedral fullerene Sc 4 C 2 @C 80 based on first-principles density-functional calculations coupled with many-body GW correction. Our calculation results yield a GW rectified gap of 1.8eV for the ‘Russian doll’ structured Sc 4 C 2 @C 80 , in very good conformity with experimental observed value of 1.6eV. The calculated electronic characteristics of the Russian-doll fullerene reveal distinct shell structures, which are embellished in the GW approach. The analysis of vibrational frequency demonstrates profound hybridizations associated with the interactions between the Sc 4 C 2 core and C 80 shell.