Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th2@C80 and U2@C80 have shown that although the two Th3+ ions form a strong covalent bond within the carbon cage, the interaction between the U3+ ions is weaker and described as an "unwilling" bond. To evaluate the feasibility of covalent U-U bonds, which are neglected in classical actinide chemistry, we have first investigated the formation of smaller diuranium EMFs by laser ablation using mass spectrometric detection of dimetallic U2@C2n species with 2n ≥ 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f3)-U(5f3) triple bonds, two U3+ ions can be incarcerated inside the fullerene. The formation of U-U bonds competes with U-cage interactions that tend to separate the U ions, hindering the observation of short U-U distances in the crystalline structures of diuranium endofullerenes as in U2@C80. Smaller cages like C60 exhibit the two interactions, and a strong triple U-U bond with an effective bond order higher than 2 is observed. Although 5f-5f interactions are responsible for the covalent interactions at distances close to 2.5 Å, overlap between 7s6d orbitals is still detected above 4 Å. In general, metal ions within fullerenes should be regarded as templates in cage formation, not as statistically confined units that have little chance of being observed.