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A detailed investigation on photoluminescence properties and energy transfer (ET) dynamics of Ce 3+ , Pr 3+ -doped BaY 2 Si 3 O 10 is provided along with the potential X-ray excited luminescence application. The luminescence properties of Pr 3+ are studied in VUV-UV-vis spectral range at low temperature, and the spectral profiles of Pr 3+ 3 P 0 and 1 D 2 emission lines are determined using time-resolved emission spectra. Upon 230 nm excitation, the electron population from Pr 3+ 4f5d state to its 4f 2 excited state is discussed in detail. As Pr 3+ concentration rises, Pr 3+ 3 P 0 and 1 D 2 luminescence possess different concentration-related properties. The incorporation of Ce 3+ in the codoped sample produces the strong Ce 3+ luminescence under 230 nm excitation, which is the combined result of Pr 3+ 4f5d → Ce 3+ 5d ET and Ce 3+ intrinsic excitation. On the other hand, the increasingly strong ET of Ce 3+ 5d → Pr 3+ 4f 2 results in the decrease of Ce 3+ emission intensity and the gradual deviation of Ce 3+ 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 C DA is determined to be 9.97 × 10 -47 m 6 ·s -1 . Finally, the relatively low scintillation light yield of Ce 3+ -doped BaY 2 Si 3 O 10 material impedes its application potential in the scintillator field, and the cosubstitution of Pr 3+ results in the observable decline of scintillation performance.