In this study, the Fenton/adsorption of dye effluent containing Levafix blue dye has been carried out via a cost-efficient and eco-friendly heterogeneous Fenton and solar-Fenton methods. Alum sludge, the water treatment by-product were successfully collected and calcined to 400 °C (AS400) were tested for use as a catalyst in the Fenton process. X-ray diffraction, Scanned electron microscopy techniques were applied to investigate the structural and morphological properties of such catalyst. The results showed that the material had a better photocatalytic activity under sunlight irradiation. The process of solar photo-Fenton reagent including AS400 was found to be competent for the oxidation of Levafix dye compared with the process of using Fenton process. The oxidation was improved to a great extent from 60 to 99% removal in the treatment time of 40-min irradiation. The key factor is containing 1.5 g/L and 800 mg/L of AS400 and H2O2, respectively, at pH 3.0. As a result, the practical application of such a by-product as a catalyst on the Fenton system employing natural solar radiation on the treating dye effluent indicates that technique is extremely efficient for a safer environment.