The intramolecular SeN interactions between the selenium and the nitrogen atom in three series of o-substituted organoselenium compounds has been studied using density functional theory (DFT). The nature and the strength of these interactions and their dependence on substituents, the chelate ring size as well as the rigidity are predicted using a B3LYP/6-31G(d)/LanL2DZ method. The strength of the SeN interactions is found to be dependent on the nature of Se–X (X = Cl, Br, I, SPh, CH₂Ph; Ph: Phenyl) acceptor orbitals and follow the order I > Br > Cl > SPh > CH₂Ph. The natural bond orbital (NBO) analysis using DFT methods points to n_N→σ^*_Se–X electron delocalization as the key contributing factor towards SeN nonbonding interactions. Both NBO and atoms in molecules (AIM) methods suggest that the intramolecular interaction in the organoselenium compounds is dominantly covalent in nature. Studies on the effect of solvent on the SeN interaction show that a polar solvent stabilizes the SeN interactions by shortening the SeN distances.