In nature, the elements of the inorganic part of the periodic table are found in three forms: metals, ions in salts & minerals, and ions in solution. The ions may be coordinated to simple or complicated ligands. They may form purely electrostatic or partially covalent bonds. A common trend is that the more covalent bonds an element form, the more we know of its physicochemical properties. The rare earths form purely electrostatic bonds, thus, our understanding of the solution chemistry of these elements is limited—yet important. Most rare earth elements used today pass through hydrometallurgical processes that rely on the solution chemistry of these elements, even through the critical applications are in alloys and functional materials. Through developments in optical spectroscopy, total X-ray scattering, and quantum chemical methods we are posed to remedy this situation: we are ready to create predictive structure–property relationships in the field of lanthanide solution chemistry. The scope of this review is to summarise the state-of-the-art for neodymium(III), to go through the structure–property relationships that are in use. In the form of NdFeB magnets, neodymium plays a crucial role in green energy production and electric propulsion. As a 4f3 ion in solution it is also one of the simpler rare earth ions, and the Nd(III) ion has characteristic optical properties that can be exploited as a handle in physicochemical studies. Here, we start with a critical review of the current concepts used to relate structure and electronic energy levels. We follow with our suggested approach of using the methodology from molecular photophysics to relate optical properties and structure, and conclude with selected literature examples.