It was unusual for Bi3+ ions to enhance the emission intensity of phosphors via nonsensitization. Here, La2MoO6:Eu3+, Bi3+ phosphors were successfully synthesized by a high temperature solid‐state reaction method in air atmosphere. As the increase of doping concentration of Bi3+, the emission spectra of La2MoO6:Eu3+, Bi3+ phosphors had obvious shifts, splits and the enhancement of intensities, which indicated that the characteristics of the phosphors were modified. To analyze these phenomena, the crystal structure refinements, spectral characteristic analyze and Judd‐Ofelt theoretical calculation were mainly performed. Bi3+ ions played the role of the nonsensitizer and affected the distortion of the crystal, the sites of Eu3+ ions, the field splitting energy and the internal quantum yield. Moreover the nephelauxetic effects of Bi3+ ions and the ET process caused synergistically the life times of La2MoO6:Eu3+, Bi3+ phosphors to increase and then gradually decrease. The CIE coordinates of phosphors changed within a small range. This study might be instrumental in promoting the further application of Bi3+ ions in rare earth luminescent materials.