Here we report the observation of near-infrared persistent luminescence (NIR PersL) of Yb3+ in perovskite CaTiO3. Sensitized by the Bi3+ codopants, it exhibits intense NIR PersL of Yb3+ at about 1000 nm. In addition, this phosphor can be excited by the near ultraviolet and even visible light, and the PersL signals can be recorded for more than 80 h. The PersL enhancement by Bi3+ is revealed to be due to the suitable Bi3+ induced deeper traps and the possible PersL quantum cutting. The results suggest that the NIR PersL of the CaTiO3:Yb3+, Bi3+ phosphor has potential applications for biomedical imaging in the second biological window.