Currently, the development of efficient red-emitting persistent phosphor is still an ongoing challenge. Herein, a novel red-emitting LPL phosphor Ca3Ti2O7:Pr3+ is successfully prepared by a high-temperature solid-state method. XRD Rietveld refinement analyses demonstrate the high phase purity of the sample which crystallizes in an orthorhombic Ccm2(1) space group with lattice parameters of a = 5.7702(5) angstrom, b = 19.4829(7) angstrom, and c = 5.1214(2) angstrom. Electronic structure of the host matrix is analyzed by the first-principle calculation using CASTE? code. The calculation results show that Ca3Ti2O7 has a direct band gap with CB and VB mainly composed of the Ti-3d and O-2p states, respectively. On the basis of the DR spectrum, the band gap is determined to be 3.6 eV. It is demonstrated that the 612 nm red-emitting persistent luminescence of Ca3Ti2O7:Pr3+ can be either activated by Ti4+-O2- -> Ti3+-O- host absorption and Pr3+-O-Ti4+ -> Pr4+-O-Ti3+ IVCT in the UV region, or Pr3+:H-3(4) -> 3P(J). transition in the blue region. The red afterglow can last for similar to 5 min observed by the naked eyes in the dark after ceasing the irradiation source. On the basis of the TL analyses, the trap is found exponentially distributed in the host with the depth of 0.69-0.92 eV. Finally, a possible LPL mechanism for Ca3Ti2O7:Pr3+ is proposed.