Yellow/orange-emitting nitrogen-rich Ca0.9Si9Al3(O,N)16: Eu2+ phosphors were successfully prepared by solid-state reaction synthesis. The fluorescence excitation spectra of all of the nitrogen-rich Ca0.9Si9Al3(O,N)16: Eu2+ phosphor powders displayed two broad bands centered at about 300 nm and 400–475 nm. The first peak was assigned to the absorption of the host lattice and the second to the 4f7 → 4f65d1 absorption of the Eu2+ ions, its means enhanced 4f7 → 4f65d excitation of Eu2+ ion. The absorption peak intensity increased upon increasing the Eu2+ doping amount, but only up to a Eu2+ concentration ratio of 0.15. The emission spectra of the prepared Ca0.9Si9Al3(O,N)16: Eu2+ phosphors all exhibited a single broad band in the 500–700 nm region, maximum emission peak observed at 591 nm. The room temperature decay times were observed τ1 = 1.27 μs and τ2 = 9.90 μs.