Pure and Cr3+-doped hydroxyapatite (HAP) were prepared via chemical precipitation route. The XRD measurements revealed that the typical HAP powder pattern was obtained. SEM analysis indicated that aggregates of nanoparticles were formed. EDX analysis indicates that the [Ca]/[P] concentration ratio was higher than the expected values but can be explained by the presence of carbonate groups as dopants. The optical absorption spectra of the doped samples presented absorption bands typical of Cr3+ occupying to different crystalline sites. From the position of the bands, it was possible to estimate the crystal field parameters for both sites of Cr3+ in the HAP matrix. The emission spectra of the Cr-doped samples were also investigated and typical transitions of the dopant ion, in trivalent state, were identified. The potential use of the Cr3+-HAP as fluorescent probes for medical applications was discussed.