Incorporating heteroatoms in functional materials is an invaluable approach to modulate their properties, assuming a solid solution is formed. However, thorough understanding of key structural information on the resulting solid solution, such as the local environment of cations and vacancies, remains a challenge. Solid-state NMR (SSNMR) spectroscopy is a powerful structural characterization tool, very sensitive to the local environment. Due to the difficulty in signal acquisition and spectral interpretation, SSNMR spectroscopy is relatively less known to chemists and materials scientists. Herein, we present an introductory review to demonstrate how to use 89 Y SS NMR spectroscopy to unravel the mystery of solid solutions. In general, 89 Y chemical shift varies with different cation/vacancy arrangements in Y coordination spheres, providing ultrafine structural information in the atomic scale. As a case study and an extreme condition, the approach demonstrated in this review can be extended to other systems.