Syntheses and structural elucidations of a series of chalcogen stabilized binuclear complexes of group 5 and 6 transition metals have been described. Room temperature reaction of [Cp^*CrCl]₂ (Cp^* = h⁵- C₅Me₅) with Li[BH₃(SePh)] afforded a Se inserted binuclear chromium complex, [(Cp^*Cr)₂(m-Se₂SePh)₂], 1.In an attempt to make the analogous complexes with heavier group 6 metals, reactions of [Cp^*MCl₄] (M = Mo and W) with Li[BH₃(SePh)] were carried out that yielded Se inserted binuclear complexes [(Cp^*M)₂(m-Se)₂(m-SePh)₂], 2 and 3 (2: M = Mo and 3: M = W) along with known [(Cp^*M)₂B₅H₉], 4a–b (4a: M = Mo and 4b: M = W). Similarly, the reactions of [Cp^*NbCl₄] with Li[BH₃(EPh)] (E = S or Se)followed by thermolysis led to the formation of binuclear chalcogen complexes [(Cp^*Nb)₂(m-E₂)₂], 5 and 6 (5: E = S and 6: E = Se) and known [(Cp^*Nb)₂(B₂H₆)₆], 7. All these complexes have been characterized by ¹H and ¹³C NMR spectroscopy and mass spectrometry. The structural integrity of complexes 1, 3, 5 and 6 was established by the X-ray diffraction studies. The DFT studies further exemplify the bonding interactions present in these complexes, especially the multiple bond character between the metals in 1–3.