The composite α-FeOOH nanorods/Ag3PO4 photocatalyst has been successfully fabricated through a facile hydrothermal process combined with a successive in situ precipitation technique. The SEM and TEM images show that Ag3PO4 particles have been successfully loaded on the surface of FeOOH nanorods. The photocatalytic activities of the α-FeOOH/Ag3PO4 composite were investigated for their efficiency on the degradation of Rhodamine B (RhB) under ultra-violet light and visible light irradiation, and the results showed that the α-FeOOH/Ag3PO4 composite possessed remarkable photocatalytic activities. The enhanced photocatalytic activity can be attributed to the strong absorption in visible light and the effective separation of photogenerated hole–electron pairs between Ag3PO4 and α-FeOOH.