The first solid-state NMR investigation of dichalcogenoimidodiphosphinato complexes, M[N(R2PE)2]n, is presented. The single-source precursors for metal-selenide materials, M[N(iPr2PSe)2]2 (M = Zn, Cd, Hg), were studied by solid-state 31P, 77Se, 113Cd, and 199Hg NMR at 4.7, 7.0, and 11.7 T, representing the only 77Se NMR measurements, and in the case of Cd[N(iPr2PSe)2]2113Cd NMR measurements, to have been performed on these complexes. Residual dipolar coupling between 14N and 31P was observed in solid-state 31P NMR spectra at 4.7 and 7.0 T yielding average values of R(31P,14N)eff = 880 Hz, CQ(14N) = 3.0 MHz, 1J(31P,14N)iso = 15 Hz, α = 90°, β = 26°. The solid-state NMR spectra obtained were used to determine the respective phosphorus, selenium, cadmium, and mercury chemical shift tensors along with the indirect spin–spin coupling constants: 1J(77Se,31P)iso, 1J(111/113Cd,77Se)iso, 1J(199Hg,77Se)iso, and 2J(199Hg,31P)iso. Density functional theory magnetic shielding tensor calculations were performed yielding the orientations of the corresponding chemical shift tensors. For this series of complexes the phosphorus magnetic shielding tensors are essentially identical, the selenium magnetic shielding tensors are also very similar with respect to each other, and the magnetic shielding tensors of the central metals, cadmium and mercury, display near axial symmetry demonstrating an expected deviation from local S4 symmetry.