Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f1 5d1 6s2 in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X‐ray absorption spectroscopy (XAS) or X‐ray absorption near‐edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L3 edge have the advantage of a high penetration depth, enabling in‐situ reaction studies in a time‐resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L3 XANES? This article provides an overview of the information that can be extracted from experimental Ce L3 XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented here together with detailed discussions on data analysis and the current status of spectral interpretation, including electronic structure calculations.