Rare-earth containing glasses are important materials with technologically relevant combinations of mechanical and optical properties. For developing their functional materials potential it is important to understand the local environment and spatial distribution of the rare-earth ions and their influence upon the structural organization of the glassy matrix. Nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) can furnish crucial information about these aspects. In this review we describe the relevant theoretical foundations with a particular focus on rare-earth containing systems. Important experimental approaches covered include dipolar NMR, paramagnetically perturbed NMR, EPR, and hyperfine interaction spectroscopies. These are illustrated in the context of various case studies, including (1) structural features of rare-earth aluminosilicate glasses, (2) spatial distribution and clustering of rare-earth dopants, (3) rare-earth ligand distributions in fluoride phosphate glasses, and structural changes along the glass-to-ceramic transformation in (4) aluminoborate and (5) oxyfluoride glasses.

含稀土玻璃是重要的材料，具有机械和光学性能的技术相关组合。为了开发其功能材料的潜力，重要的是了解稀土离子的局部环境和空间分布及其对玻璃状基质结构组织的影响。核磁共振（NMR）和电子顺磁共振（EPR）可以提供有关这些方面的重要信息。在这篇综述中，我们描述了相关的理论基础，特别关注含稀土的系统。涵盖的重要实验方法包括偶极NMR，顺磁扰动NMR，EPR和超精细相互作用光谱学。这些是在各种案例研究中说明的，