Mechanoluminescent (ML) materials are promising for applications in structural health monitoring, biomedicine, stress sensing, and stress distribution visualization due to their ability to emit light without external circuits. However, current ML materials face challenges, including limited luminescent colors, high raw material costs, toxicity, and lack of emissions in the invisible light spectrum. To overcome these challenges, Ca ₂P ₂O ₇ (CPO) is selected as the matrix material due to its excellent piezoelectric properties, low cost, and biocompatibility. CPO is doped with various luminescent ions (X, X = Ce ³⁺, Eu ^2+/3+, Tb ³⁺, Dy ³⁺, Mn ²⁺, Sm ³⁺) to achieve the emission bands of CPO:X across a wide range of wavelengths including UV, blue, green, yellow and red. Unlike traditional trap‐controlled ML materials, CPO:X does not require UV pre‐irradiation and exhibits remarkable self‐recovery properties. First‐principles …