Three-dimensional (3D) Ag–ZnFe2O4-reduced graphene oxide (rGO) was successfully synthesized using a hydrothermal and photo-reduction method, and the morphological differences of the materials were observed. Their photocatalytic activity was evaluated by photocatalytic degradation of enrofloxacin (ENR) under visible-light irradiation. The results indicated that Ag–ZnFe2O4–rGO exhibited superior photocatalytic properties and good stability. In this research, the enhancement of photocatalytic performance is mainly attributed to the electron channelization ability of rGO, which traps the photoexcited electrons of ZnFe2O4 on its π framework, and reduces the electron–hole recombination rate. Moreover, the high surface area of 3D pompon mum flower-like ZnFe2O4 provides more reactive sites. In addition, free radical capture and ESR experiments as well as pathway analysis of degradation also confirmed that superoxide radicals (˙O2−) and photo-generated holes from Ag–ZnFe2O4–rGO were the main active species in the degradation progress of ENR.
