The reaction of bis(organyl)diselenide with a reducing agent, such as LiAlH₄, NaBH₄, Li(C₂H₅)₃BH, etc., generally leads to cleavage of the Se–Se bond resulting in the formation of the corresponding organylselenols/selenolates. However, this work for the first time demonstrates the scisson of the C_(pyridine)–Se bond in bis(2-pyridyl)diselenides with LiAlH₄. The reaction affords analytically pure bis(2-pyridyl)selenides in near quantitative yields. The reaction pathway involves the formation of a selenated aluminato complex followed by the scission of the C_(pyridine)–Se bond and generation of LiAlSeH₂. The generation of LiAlSeH₂ was established by experimental and NMR analysis. The mechanism of the reaction has been supported by theoretical analysis. Single crystal X-ray structure determination of bis(3-methyl-2-pyridyl)selenide (2e) was performed and it shows that the molecules are self-assembled in a 2D-network of C–H⋯N hydrogen bonds and π⋯π stacking interactions. The synthesized compounds were also evaluated against the Raji cancer cell line (acute lymphoid leukemia).