Density functional theory (DFT) has been used to probe the bonding and electronic properties of dimolybdaborane [(Cp*Mo)(2)B5H9], 1 (Cp* = eta(5)-C5Me5), and several other hetero-dimolybdaborane clusters, such as [(Cp*Mo)(2)B-5(mu(3)-OEt)H-7] (2), [(Cp*Mo)(2)B-5(mu(3)-OEt)(n-BuO)H-6] (3), [(eta(5)-C5H5W)(2)B4H4S2] (4), and [(Cp*Mo)(2)B4H4E2] (5-7, where, for 5, E = S, for 6, E = Se, and for 7, E = Te). The DFT results were also used to address some key points such as (i) the metal-metal bond length, (ii) the location and number of bridging and terminal hydrogen atoms, (iii) the molecular orbital analysis, and (iv) the assignment of B-11 and H-1 NMR chemical shifts. These studies further provide meticulous insight into similarities and differences between various dimetallaborane clusters 1-7. In addition, the crystal structures of 5 and 7 are reported, which come on top of the already existing literature of dimetallaboranes and support the theoretical findings.