Fe2O3 nanoparticles were synthesized by green chemistry using orange peel extract. The structural characteristics of Fe2O3 were tested through analysis methods such as scanning electron microscopy, Fourier Transform Infrared Spectroscopy, and X-ray diffraction. Fe2O3 nanoparticles have a heterogeneous spherical shape with the mass ratio of iron (55.66%) and oxygen (36.86%). Crystals of Fe2O3 nanoparticles were identified as γ-Fe2O3 with a hexagonal crystal structure and size 56.66 nm (nano size) with peaks 2θ = 30.25° (220), 35.68° (311), 43.34° (400), 53.39° (422), 57.36° (511), and 63.03° (440). The peaks at 636, 554, 480, and 422 cm–1 were believed to be the existence of a metallic oxygen (Fe-O) band. In addition, the OH and C=C groups were attributed to the presence of orange peel extract. The ability of γ-Fe2O3 nanoparticles to remove Congo red was selected under the following conditions: time 30 min, temperature 50 °C, pH 6, dosage 0.05 mmol L−1, and concentration at 400 mg L−1 with maximum adsorption capacity 1417.71785 mg g−1. The pseudo-first order and pseudo-second order were suitable for the adsorption process of the material with high correlation coefficients of 0.965 and 0.956, respectively. The adsorption process fits pseudo-first-order and pseudo-second-order kinetics and were mainly controlled by physical and chemical interactions. The Freundlich and Dubinin–Radushkevitch adsorption isothermal were mainly controlled by multilayer adsorption with heterogeneous electrostatic interaction force on the surface with Gaussian energy distribution. It can be seen that γ-Fe2O3 nanoparticles from green chemistry methods are potential materials to replace materials synthesized from conventional chemical methods.