Multinuclear NMR studies of the gaseous mixtures that involve volatile compounds and ³He atoms are featured in this review. Precise analyses of the ³He and other nuclei resonance frequencies show linear dependences on the gas density. Extrapolation of the gas phase results to the zero-pressure limit gives ν₀(³He) and ν₀(ⁿX) resonance frequencies of nuclei in a single 3-helium atom and nuclei in molecules at a given temperature. The NMR frequency comparison method provides an approach for determining different nuclear magnetic moments. Application of quantum chemical shielding calculations which include a more complete and careful theoretical treatment allows the shielding of isolated molecules to be achieved with great accuracy and precision. They are used for evaluation of nuclear moments without shielding impact on bare nuclei: ^10/11B, ¹³C, ¹⁴N, ¹⁷O, ¹⁹F, ²¹Ne, ²⁹Si, ³¹P, ³³S, ^35/37Cl, ³³S , ⁸³Kr, ^129/131Xe, and ¹⁸³W. On the other hand, new results of nuclear moments were used for reevaluation of absolute nuclear magnetic shielding in molecules under study. Additionally, ³He gas in water solutions of lithium and sodium salts was used for measurements of ^6/7Li and ²³Na magnetic moments and reevaluation of shielding parameters of Li⁺ and Na⁺ water solvated cations. In this paper, guest ³He atoms that play a role in probing the electron density in many host macromolecules are presented as well.