The BaZrxSi3O7+2x:Eu2+/Eu3+ (2%, molar ratio) phosphors were prepared with adding different amounts of zirconium dioxide (ZrO2) (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) by a self‐reduction method under air conditions. X‐ray diffraction, photoluminescence properties, thermal quenching properties and luminescent lifetimes of the prepared samples were systematically analyzed. In BaZrxSi3O7+2x:Eu2+/Eu3+, both the 4f → 5d transitions of Eu2+ and sharp emissions assigned to 5D0 → 7FJ (J = 0, 1, 2, 3, 4) transitions of Eu3+ were observed. In addition, the results also reveal that the amount of ZrO2 affects the crystal structure, the self‐reduction process and further influences the relative intensity of Eu2+/Eu3+ in all samples. Therefore, the diverse emission colors can be obtained and modulated by controlling the content of ZrO2. The highlight of this work is that the white light emission is observed, when x is 0.4, 0.6, 0.8 and 1, respectively.