In this work, a saline aqueous solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a falling-film solar reactor. The influence of the parameters such as initial pH (5-7), initial concentration of Fe2+ (1-2.5mM) and rate of H202 addition (1.87-3.74mmol min-1) was investigated. The efficiency of photodegradation was determined from the removal of dissolved organic carbon (DOC), described by the species degradation of phenol, 2,4-D and 2,4-DCP. Response surface methodology was employed to assess the effects of the variables investigated, i.e. [Fe2+], [H202] and pH, in the photo-Fenton process with solar irradiation. The results reveal that the variables' initial concentration of Fe2+ and H202 presents predominant effect on pollutants' degradation in terms of DOC removal, while pH showed no influence. Under the most adequate experimental conditions, about 85% DOC removal was obtained in 180 min by using a reaction system employed here, and total removal of phenol, 2,4- and 2,4-DCP mixture in about 30min.