The photo-Fenton process was applied to degrade non-ionic surfactants with different numbers of ethoxy groups, seven (E7), ten (E10) and twenty-three (E23). The effects of H2O2 concentration, Fe(II) concentration and number of ethoxy groups on the mineralization of surfactants were investigated. The response surface methodology (RSM) was applied to determine optimal concentrations of Fenton's reagents for each surfactant. The efficiency of the photo-Fenton process reached 95% for all surfactants studied at 45 min in optimal conditions determined in this work. The analysis of results showed that the efficiency depends upon the number of ethoxy groups in the surfactant. The increase in ethoxy groups favoured the mineralization of surfactants. The analysis of variance (ANOVA) was applied, and according to the F-test the models for the mineralization of surfactants were considered significant and predictable. The photo-Fenton process has proven to be feasible for the degradation of ethoxylated surfactants in aqueous solution.