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Abstract We demonstrate that doping hydroxyapatite (HAp) with Cr³⁺ions induces oxygen vacancies, contributing to paramagnetism. Cathodoluminescence and photoluminescence analyses reveal increased oxygen vacancy formation in$${\text{O}}{\text{H}}^{-}$$ ${\text{OH}}^{-}$and$${\text{P}}{\text{O}}_{4}^{3-}$$ ${\text{PO}}_4^{3-}$groups with rising Cr³⁺concentrations, highlighted by stronger cathodoluminescence emissions at 2.57 and 2.95 eV and the photoluminescence emission at 3.32 eV. Raman spectroscopy shows new modes at 900 and 970 cm⁻¹, indicating distortion of thev₁vibrational mode due to Cr³⁺substitution at Ca(II) sites of the HAp lattice. X-ray photoelectron spectroscopy confirms Cr³⁺in the HAp:Cr. Magnetometry reveals a shift from diamagnetism in pure HAp to increasing paramagnetism in HAp:Cr with higher Cr³⁺content, achieving 0.0460 emu/g at 10 kOe with concentrations higher than 2.9 at.%. This paramagnetism is attributed to Cr³⁺ions and singly ionized oxygen vacancies$$V^{\prime}_{{\text{O}}}$$ $V_{\text{O}}^{\prime }$aligning along an external magnetic field, with$$V^{\prime}_{{\text{O}}}$$ $V_{\text{O}}^{\prime }$formation linked to$${\text{PO}}_{4}^{{3}-}$$ ${\text{PO}}_4^{3-}$replacement by$${\text{PO}}_{3}^{{2}-}$$ ${\text{PO}}_3^{2-}$in HAp.