The photoluminescence properties of silicon-based xenotime-type rare-earth phosphate as an orange-red-emitting phosphor material, SrY3SiP5O20:xEu(3+) (0.2, 0.6, 1, 2, 3, 5, 10, and 15 mol %), are reported. The photoluminescence spectra of the silicon phosphate indicated the simultaneous occurrence of six predominant orange-red band emissions due to doubly split magnetic-dipole (D-5(0)-F-7(1)), electric-dipole (D-5(0)-F-7(2)), and unusual (D-5(0)-F-7(4)) transitions under a near-UV wavelength excitation. The multiband emission of Eu3+ at D-5(0)-F-7(1,2,4) is attributed to the odd-parity distortions of the Eu3+ surrounding environment. With high Eu3+ concentration, the phosphor has a strong excitation due to f-f transitions appearing at around 396 nm, which correspond to the popular emission line from a near-UV light-emitting diode (LED) chip. Thus, the intense orange-red emission of the silicon phosphate phosphors under near-UV excitation suggests them to be a potential candidate for white light generation by using near-UV LEDs.