Organoselenium compounds find versatile applications in organic synthesis, materials synthesis, and ligand chemistry. Organoselenium heterocycles are widely studied agents with diverse applications in various biological processes. This review highlights the recent progress in the synthesis of selenium heterocycles using diorganyl diselenides with keen attention on green synthetic approaches, scopes, C-H selanylation, the mechanisms of different reactions and insights into the formation of metal complexes. The C-H selanylation using diorganyl diselenides with different catalysts, bases, transition metals, iodine salts, NIS, hypervalent iodine, and other reagents is summarised. Finally, the diverse binding modes of bis(2/4-pyridyl)diselenide with different metal complexes are also summarised.