Room-temperature reactions between [Cp*CoCl]2 (Cp∗ = ν5-C5Me5) and large excess of [BH2E3]Li (E = S or Se) led to the formation of homocubane derivatives, 1-7. These species are bimetallic tetrahomocubane, [(Cp*Co)2(μ-S)4(μ3-S)4B2H2], 1; bimetallic trishomocubane isomers, [(Cp*Co)2(μ-S)3(μ3-S)4B2H2], 2 and 3; monometallic trishomocubanes, [M(μ-E)3(μ3-E)4B3H3] [4: M = Cp*Co, E = S; 5: M = Cp*Co, E = Se and 6: M = {(Cp*Co)2(μ-H)(μ3-Se)2}Co, E = Se], and bimetallic homocubane, [(Cp*Co)2(μ-Se)(μ3-Se)4B2H2], 7. As per our knowledge, 1 is the first isolated and structurally characterized parent prototype of the 1,2,2′,4 isomer of tetrahomocubane, while 3, 4, and 5 are the analogues of parent D3-trishomocubane. Compounds 2 and 3 are the structural isomers in which the positions of the μ-S ligands in the trishomocubane framework are altered. Compound 6 is an example of a unique vertex-fused trishomocubane derivative, in which the D3-trishomocubane [Co(μ-Se)3(μ3-Se)4B3H3] moiety is fused with an exopolyhedral trigonal bipyramid (tbp) moiety [(Cp*Co)2(μ-H)(μ3-Se)2}Co]. Multinuclear NMR and infrared spectroscopy, mass spectrometry, and single crystal X-ray diffraction analyses were employed to characterize all the compounds in solution. Bonding in these homocubane analogues has been elucidated computationally by density functional theory methods. © 2019 American Chemical Society.