The existence or presence of diverse hydrocarbons and persistent pollutants in seawater or saline wastewater due to different industrial activities is considerable. The photo-Fenton process is suggested as a possible treatment, but the effect of salinity must be explored. An experimental design is carried out to elucidate the influence of NaCl on the efficiency of the process. According to the results, the global TOC removal is not influenced by the presence of chloride, but the process becomes much slower, even more than 10 times in some of the operating conditions. If solar irradiation is possible photo-Fenton seems a good option to treat polluted water with high salinity.