Density functional theory (DFT) has been used to probe the bonding and electronic properties of dimolybdaborane [(Cp*Mo)(2)B(5)H(9)], 1 (Cp* = η(5)-C(5)Me(5)), and several other heterodimolybdaborane clusters, such as [(Cp*Mo)(2)B(5)(μ(3)-OEt)H(7)] (2), [(Cp*Mo)(2)B(5)(μ(3)-OEt)(n-BuO)H(6)] (3), [(η(5)-C(5)H(5)W)(2)B(4)H(4)S(2)] (4), and [(Cp*Mo)(2)B(4)H(4)E(2)] (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 (11)B and (1)H 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.