The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe2+ under UV irradiation of the iron complex and the photochemical formation of HO• from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H2O2 concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe2+ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H2O2 concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.