A novel pale-yellow Ba2ZnGe2O7:Bi3+ phosphor with site-selected excitation and small thermal quenching was synthesized by conventional solid-state sintering. The crystal structure and luminescence properties have been investigated in detail for the first time using XRD patterns, photoluminescence spectra, diffuse reflection spectra, decay curves, and temperature-dependent emission spectra. The results reveal that the excitation spectrum of Ba2ZnGe2O7:Bi3+ phosphor locates in the near-ultraviolet region of 300-400 nm, and its emission shows an obvious site-selective excitation phenomenon since Bi3+ ions occupy two different crystallographic sites in the Ba2ZnGe2O7 host. When excited under 360 nm, the phosphors show a pale-yellow emission in the range of 400-700 nm with the maximum peaking at 520 nm, while when excited under 316 nm, the phosphors show a blue emission in the range of 400-700 nm with the maximum peaking at 480 nm. In addition, the emission of Ba2ZnGe2O7:Bi3+ can also be easily controlled by changing the Bi3+ concentration. The Ba2ZnGe2O7:Bi3+ phosphor has small thermal quenching, and its emission intensity only decreases by 2% at 200 degrees C. The results indicate that this novel pale-yellow Ba2ZnGe2O7:Bi3+ phosphor could be conducive to the development of white light-emitting diodes.