Through the order–disorder transition process of zeolites, bismuth‐doped zeolite‐derived silica glasses with broadband near‐infrared (NIR) photoluminescence have been successfully prepared by spark plasma sintering (SPS). The samples were characterized by X‐ray diffraction, UV‐vis, photoluminescence, and fluorescence lifetime. The results showed that as‐prepared samples possessed favorable broadband NIR luminescence. The NIR emission (peaked at ~1140 nm) intensity decreased with increasing the bismuth doping concentration when excited by 500 and 700 nm. The tendency was different from the emissions (peaked at ~1240 nm) excited by 800 nm. In addition, the NIR fluorescence peaks of the fixed Bi concentration sample can be observed almost around 1140 or 1240 nm when excited by different wavelengths from 500 to 950 nm. These phenomena implied that the NIR emission peaked at different wavelengths may originate from different bismuth species. Three kinds of Bi active centers Bi+, Bi0, and (Bi2)2− were proposed to contribute to the NIR emission peaks at ~1140, 1240, and 1440 nm, respectively. Interestingly, a broadband NIR emission peaked at 1207 nm with a full‐width at half maximum of 273 nm was observed when excited by 600 nm, whose intensity was stronger than that excited by 800 nm. This property might be useful for broadband fiber amplifiers and tunable lasers.