In this study, a heterogeneous photo-Fenton catalyst of Fe species/resorcinol-formaldehyde (Fe/RF) was synthesized in the degradation process of phenols under visible light in a homogeneous photo-Fenton system. The in situ generated HO by bare RF in the medium and the follow-added Fe can construct homogeneous photo-Fenton system, and Fe/RF heterogeneous photo-Fenton catalyst was formed after the reaction through Fe species self-deposition. Due to the addition of Fe, more hydroxyl radical (·OH) generated in the homogeneous Fenton system, which lead to the higher degradation efficiency of phenols that achieved 90.5 % with 150 min. Fe/RF was subsequently formed and more C=O functional group in the structure appeared, which was beneficial to the production of HO. The above-mentioned results can be proved by the involved calculation and experimental results. Fe species, including Fe and Fe, were beneficial to the conversion of reactive oxygen species (ROSs), and further improved the degradation efficiency of Phenols. Since the existence of photo-generated electrons, Fe concentration in the solution can maintain a stable level. Interestingly, the degradation efficiency of Phenols was higher when Fe was used instead of Fe as the additive, which may be caused by the promotive effect of Fe on singlet oxygen (O) generation. In addition, the degradation efficiency of Phenols under alkaline conditions was higher than that under acid conditions, which broke the limit of traditional Fenton process that works mostly in acidic medium. This study shows promising results in terms of synergistic photocatalytic/photo-Fenton processes for the degradation of organic pollutants in water.