Spherical Bi₂MoO₆ nanoarchitectures with scale of 500 nm–2 μm were prepared by a solvothermal reaction using bismuth nitrate and ammonium molybdate as precursors. Ag₃PO₄ nanoparticles were then deposited onto the surface of Bi₂MoO₆via a facile deposition–precipitation technique. The photocatalytic tests display that the Ag₃PO₄/Bi₂MoO₆ nanocomposites possess a much higher rate for degradation of rhodamine B and methylene blue than the pure Ag₃PO₄ nanoparticles and Bi₂MoO₆ under visible light. The catalytic activity of the composite photocatalysts is greatly influenced by the loading level of Ag₃PO₄. The 50 mol% Ag₃PO₄-loaded Bi₂MoO₆ spheres exhibit the highest photocatalytic activity in both the decolorization of RhB and MB. The observed improvement in photocatalytic activity is associated with the extended absorption in the visible light region resulting from the Ag₃PO₄ nanoparticles, and the effective separation of photogenerated carriers at the Ag₃PO₄/Bi₂MoO₆ interfaces. In addition, the composite can be easily reclaimed by sedimentation without any loss of its stability. Moreover, the tests of radical scavengers confirmed that h⁺ and ˙OH were the main reactive species for the degradation of RhB.