A detailed investigation on photoluminescence properties and energy transfer (ET) dynamics of Ce3+, Pr3+-doped BaY2Si3O10 is provided along with the potential X-ray excited luminescence application. The luminescence properties of Pr3+ are studied in VUV-UV-vis spectral range at low temperature, and the spectral profiles of Pr3+ 3P0 and 1D2 emission lines are determined using time-resolved emission spectra. Upon 230 nm excitation, the electron population from Pr3+ 4f5d state to its 4f2 excited state is discussed in detail. As Pr3+ concentration rises, Pr3+ 3P0 and 1D2 luminescence possess different concentration-related properties. The incorporation of Ce3+ in the codoped sample produces the strong Ce3+ luminescence under 230 nm excitation, which is the combined result of Pr3+ 4f5d → Ce3+ 5d ET and Ce3+ intrinsic excitation. On the other hand, the increasingly strong ET of Ce3+ 5d → Pr3+ 4f2 results in the decrease of Ce3+ emission intensity and the gradual deviation of Ce3+ luminescence decay from the single exponential in the system. By employing the Inokuti-Hirayama model, the dipole-dipole interaction is confirmed as the predominant multipolar effect in controlling this ET process, and the value of CDA is determined to be 9.97 × 10-47 m6·s-1. Finally, the relatively low scintillation light yield of Ce3+-doped BaY2Si3O10 material impedes its application potential in the scintillator field, and the cosubstitution of Pr3+ results in the observable decline of scintillation performance.