Near-infrared (NIR) persistent luminescence (PersL) materials have unique optical properties with promising applications in bioimaging and anticounterfeiting. However, their development is currently hindered by poor red-light-exciting ability. In this study, CaTiO 3 :Cr 0.001 ,Y 0.02 (CTCY) was synthesized with 650 nm-excited 772 nm NIR PersL. The Y 3+ doping in the Ca 2+ lattice plays a key role in the PersL property. A charge compensation mechanism was proposed, in which Cr 3+ in the Ti 4+ lattice was stabilized by Y 3+ -doping while oxygen vacancies were generated to store the excitation energy at the same time. A thermal ionization mechanism might elucidate the red-light-excited NIR PersL of CTCY, which benefits from the perovskite structure of CaTiO 3 . CTCY has 120 times more intense red-light-excited PersL than Zn 3 Ga 2 Ge 2 O 10 :Cr. Its potential applications in luminescence anticounterfeiting and bioimaging were demonstrated using a visible/NIR dual-channel PersL flower painting and a CTCY-labeled bone screw for in situ reactivable PersL imaging using red light illumination instead of X-ray, respectively. This study not only provides a new NIR PersL material but also will add to our understanding in developing other potential red-light-or even NIR-activable PersL materials with perovskite-like structures.