To advance the understanding of the chemical behavior of actinides, a series of trans-bis(imido) uranium(VI) complexes, U(NR)2(THF) 2(cis-I2) (2R; R = H, Me, tBu, Cy, and Ph), U(NR)2(THF)3(trans-I2) (3R; R = H, Me, tBu, Cy, and Ph) and U(NtBu)2(THF) 3(cis-I2) (3tBu′), were investigated using relativistic density functional theory. The axial U =N bonds in these complexes have partial triple bonding character. The calculated bond lengths, bond orders, and stretching vibrational frequencies reveal that the U =N bonds of the bis-imido complexes can be tuned by the variation of their axial substituents. This has been evidenced by the analysis of electronic structures. 2H, for instance, was calculated to show iodine-based high-lying occupied orbitals and U(f)-type low-lying unoccupied orbitals. Its U =N bonding orbitals, formed by U(f) and N(p), occur in a region of the relatively low energy. Upon varying the axial substituent from H to tBu and Ph, the U =N bonding orbitals of 2tBu and 2Ph are greatly destabilized. We further compared the U =E (E = N and O) bonds of 2H with 3H and their uranyl analogues, to address effects of the equatorial tetrahydrofuran (THF) ligand and the E group. It is found that the U =N bonds are slightly weaker than the U =O bonds of their uranyl analogues. This is in line with the finding that cis-UNR 2 isomers, although energetically unfavorable, are more accessible than cis-UO2 would be. It is also evident that 2H and 3H display lower U =(NH) stretching vibrations at 740 cm-1 than the U =O at 820 cm-1 of uranyl complexes. With the inclusion of both solvation and spin-orbit coupling, the free energies of the formation reactions of the bis-imido uranium complexes were calculated. The formation of the experimentally synthesized 3Me, 3Ph, and 2tBu are found to be thermodynamically favorable. Finally, the absorption bands previously obtained from experimental studies were well reproduced by time-dependent density functional theory calculations.