We have investigated the potential energy curves (PECs) of the LiN heteronuclear diatomic molecule, including its ionic species LiN⁺ and LiN⁻, using explicitly correlated multi-reference configuration interaction (MRCI-F12) calculations in conjunction with the correlation consistent quintuple-𝜁 basis set. The effect of core–valence correlation, scalar relativistic effects, and the size of the basis sets has been investigated. A comprehensive set of spectroscopic constants determined based on the above-mentioned calculations are also reported for the lowest electronic states and all systems, including dissociation energies, harmonic and anharmonic vibrational frequencies, and rotational constants. Additional parameters, such as the dipole moments, equilibrium spin-orbit constants, excitation energies, and rovibrational energy levels, are also documented. We found that the three triplet states of LiN, namely, X ³∑⁻, A ³Π, and 2 ³∑⁻, exhibit substantial potential wells in the PEC diagrams, while the quintet states are repulsive in nature. The ground state of the anion also shows a deep potential well in the vicinity of its equilibrium geometry. In contrast, the ground and excited states of the cation are very loosely bound. Charge transfer properties of each of these states are also analyzed to obtain an in-depth understanding of the interatomic interactions. We found that the core–valence correlation has a substantial effect on the calculated spectroscopic constants.@en