Photochemical advanced oxidation processes (AOPs) utilising different Fenton systems were investigated in laboratory-scale experiments for the degradation of polyethylene glycol (PEG). The results of the study showed that the degradation rate of PEG was strongly accelerated by the homogeneous system, and this proved to be advantageous in comparison to the heterogeneous system. Between Fenton and photo-Fenton heterogeneous systems, the photo-Fenton process reached the highest removal rate of the organic compound, due to the enhanced reduction efficiency of Fe(III) to Fe(II) under UV-irradiation. The oxidation rate in the heterogeneous system was investigated using varying different parameters, such as the pH value, the concentration of hydrogen peroxide and the amount of Fe(OH)3 as the catalyst. For the homogeneous Fenton system the rate of degradation is significantly higher. At the same time of operation the elimination rates can be found to be 30% over the rates of the heterogeneous system. Optimising the typical influence parameters mentioned before, a degradation of about 93% of PEG can be achieved by using the homogeneous Fenton system.