© 2017 The Author(s). Endohedral metallofullerenes, formed by encaging Gd inside fullerenes like C 80 , can exhibit enhanced proton relaxitivities compared with other Gd-chelates, making them the promising contrast agents for magnetic resonance imaging (MRI). However, the underlying key energy scales of Gd x Sc 3-x [email protected] 80 (x = 1-3) remain unclear. Here, we carry out resonant inelastic X-ray scattering (RIXS) experiments on Gd x Sc 3-x [email protected] 80 at Gd N 4,5 -edges to directly study the electronic structure and spin flip excitations of Gd 4f electrons. Compared with reference Gd 2 O 3 and contrast agent Gadodiamide, the features in the RIXS spectra of all metallofullerenes exhibit broader spectral lineshape and noticeable energy shift. Using atomic multiplet calculations, we have estimated the key energy scales such as the inter-site spin exchange field, intra-atomic 4f-4f Coulomb interactions, and spin-orbit coupling. The implications of these parameters to the 4f states of encapsulated Gd atoms are discussed.