AbstractCore/shell structures are widely employed to enhance photoluminescence efficiency and manipulate excitation dynamics in lanthanide‐doped fluoride nanoparticles (NPs). However, prominent cation intermixing leads to significant deviations from the expected optical performances, presenting a formidable challenge in a deeper understanding of the chemical processes involved, as well as developing efficient suppression methods. Here, a reliable and facile multi‐optical reference strategy to reveal the integral cation intermixing processes is designed. This strategy analyzes the presence of Ce3+ ions in the core (or shell) and their influences on near‐infrared light‐triggered upconversion (UC), ultraviolet (UV)‐activated downshifting (DS), and X‐ray‐excited optical/persistent luminescence (XEOL/XEPL) of Tb3+ ions in the shell (or core). The results demonstrate that a thin surface layer of core NPs dissolves to reach dissolution equilibrium, which then distributes throughout the entire shell layer, rather than being confined to an interfacial region. It is further developed an improved technique to greatly inhibit cation intermixing by successive shell growth with excessive cation precursors, enabling superior multi‐optical performances, including UC, DS, XEOL/XEPL, and time‐dependent multicolor evolution. The findings significantly advance the development of lanthanide‐doped fluoride core/shell NPs with superior optical performances, broadening their potential applications in bio‐medicine, healthcare, industrial inspection, and optical information science.