Flower-like AgI/Bi5O7I hybrid photocatalysts were fabricated via a hydrothermal method and the subsequent heating process with AgI/Bi4O5I2 as the intermediate. X-ray powder diffraction, Raman, X-ray photoelectron spectroscopy, diffuse reflectance spectra, scanning electron microscopy, transmission electron microscopy, photoluminescence, and electrochemical methods were used to reveal the structure, elemental content, morphology, and charge separation capabilities of the as-prepared samples. The photocatalytic test showed that the AgI/Bi5O7I composites own much higher photoactivity than pure AgI and Bi5O7I. Based on the result of XPS analysis, the composite is believed to be the Ag/AgI/Bi5O7I system. Due to the suitable band potentials of AgI and Bi5O7I, the ternary system can form a heterojunction structure which works in a Z-scheme mechanism with Ag nanoparticles as the transfer media. The guided charge transfer in the composite prolongs the life time of charge carriers and eventually leads to the high photocatalytic activity of AgI/Bi5O7I. Additionally, the flower-like structure of the composite also contributes to the photocatalytic reaction.