Searching for biocompatible materials with proper luminescent properties is of fundamental importance, as they can be applied in fluorescent labeling and regenerative medicine. In this study, we obtained new phosphate–vanadate hydroxyapatites (abbr. HVps) co-doped with Sr2+ and Tb3+ ions via the hydrothermal method. We focused on examining the effect of various annealing temperatures (500, 600 and 700 °C) on the spectroscopic properties and morphology of the obtained HVps. To characterize their morphology, XRPD (X-ray powder diffraction), SEM-EDS (scanning electron microscopy–energy-dispersive spectrometry), FT-IR (Fourier transform infrared) spectroscopy and ICP-OES (inductively coupled plasma–optical emission spectrometry) techniques were used. A further study of luminescent properties and cytocompatibility showed that the obtained HVps co-doped with Sr2+ and Tb3+ ions are highly biocompatible and able to enhance the proliferation process and can therefore be potentially used as fluorescent probes or in regenerative medicine.