In this article, lanthanum molybdenum oxides (La2MoO6 and La2Mo2O9) and their Bi-doped derivatives were investigated as potential rare-earth-free phosphors. An X-ray diffraction analysis coupled with an EDX study confirmed the purity of the samples and the insertion of bismuth in a 1 molar % amount. Kubelka–Munk-transformed reflectance spectra clearly indicated that the insertion of Bi induces a shortening of the optical gap in La2MoO6 but has no impact on that of La2Mo2O9. Moreover, excitation and emission spectra evidenced a strong temperature quenching effect in all materials. Also, the CIEx,y parameters at 77 K are almost identical with or without Bi doping for the two host lattices. Clearly, it was shown, by combining experimental data, ab initio calculations, and the empirical positioning of absorption bands that the luminescence of the Bi-doped La2MoO6 sample is mainly related to the host lattice itself and distortions induced by La/Bi substitution. The role of the Bi3+ dopant is indirect, and the luminescence is mainly due to a Mo–O charge transfer rather than an on-site Bi3+3P1,0 → 1S0 transition. Concerning La2Mo2O9, there is no effect following the insertion of Bi, implying that the role of Bi is insignificant.