Stimulated by the recent successful synthesis and crystallographic characterization of the first diuranium carbide endohedral metallofullerene (EMF) U2C@Ih(7)-C80 ( Zhang et al. Nat. Commun. ; 2018 ), density functional theory calculations were performed for a series of U2C@C2n (2n = 60, 68, 72, 78, 80, 88, 96, and 104) analogues. The internal UCU bond angle increases from 96.9° in Ih-C60 to 180.0° in D3d-C104, exhibiting cage-size-dependent cluster configuration. However, further evidence suggests that the U2C shape may be also affected by the amount of charge transferred from the cluster to the outer cage with 6e and 4e favoring bent and linear, respectively. The change of the bond angle closely correlates with the charge and hybrid state of the internal atom. Significantly, besides the covalent two-center two-electron (2c-2e) U-C bonds, the U2C unit always features two 3c-2e bonds regardless of its size, shape, and charge state. Furthermore, for the cluster-cage interactions, besides the dominated electrostatic attractions, all these EMFs show an obvious covalent character with the substantial participation of U 5f valence orbitals.