A preliminary study involving solid-state 77Se NMR spectroscopy and first principles calculations of 77Se NMR parameters in Se–N heterocycles is reported. 77Se CP/MAS NMR spectra of the ring systems reveal expansive selenium chemical shift (CS) tensors, which are extremely sensitive to molecular geometry, symmetry, ligand substitution, and intermolecular contacts. For systems with known crystal structures, hybrid density functional theory (DFT) calculations of selenium nuclear magnetic shielding (NMS) tensors were carried out, and tensor orientations in the molecular frames examined. Additional DFT calculations of selenium NMS tensors are presented, along with a detailed analysis of pairs of occupied and virtual molecular orbitals that give rise to the Se NMS tensors. A new naturalized local molecular orbital (NLMO) analysis under the same DFT framework is also discussed. Collectively, the NMR data and first principles calculations provide understanding of the influences of electronic structure, bonding, and intermolecular interactions on the selenium NMS tensors, allowing for (i) prediction of unknown molecular structures and (ii) insight into the positions of the stereochemically active selenium lone pairs.