The emergence of bismuth molybdate (Bi2MoO6) as a promising visible-light catalyst has prompted researchers to increasingly focus on its investigation. To elucidate the impact of different preparation methods on the morphology and photocatalytic properties of Bi2MoO6, samples were synthesized via solvothermal, in situ conversion, solution combustion, precipitation, and sol-gel techniques. The physicochemical properties of Bi2MoO6 were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), particle size analysis (PSA), fluorescence, and photocurrent measurements. The materials’ ability to degrade Rhodamine B (RhB) was evaluated. The results demonstrated that the crystallinity, morphology, bandgap width, and photogenerated carrier recombination of Bi2MoO6 varied significantly depending on the preparation method. Among these methods, the solvothermal route proved most effective, yielding Bi2MoO6 with the highest photocatalytic activity, achieving 97.5% RhB degradation within 25 min of light exposure. The low photogenerated carrier recombination rate was attributed to the large specific surface area and narrow bandgap (2.71 eV). This study provides valuable insights into preparing Bi2MoO6 with enhanced photocatalytic properties.