In this manuscript, a novel reduced graphene oxide nanosheet/FexOy/nitrogen-doped carbon layer (rGS/FexOy/NCL) aerogel with FexOy NPs sandwiched between rGS and NCL was prepared via a two-step method. Their catalytic performance was evaluated in a photo-Fenton degradation of rhodamine B. It was found that rGS/FexOy/NCL aerogel represented higher degradation activity than the sum of rGS/NCL support and FexOy NPs, suggesting synergistic effect was established between support and reactive species. The degradation activity was investigated on the basis of aerogel usage, FexOy loading, H2O2 dosage, pH value and RhB concentration. To test stability and reusability, leaching experiments, cyclic experiments and structural analysis were carried out. Based on inhibitor experiment and intermediate detection, a possible catalytic mechanism and degradation pathway of RhB were proposed.