A novel solar-wastewater-energy recovery system was presented to simultaneously remove refractory organic pollutants from saline wastewater and produce energy. To accomplish this goal, a two-chamber cell was fabricated. The anode chamber integrating photo-oxidation and flocculation was developed by using a TiO2 nanotube array (TNA) and Al foil. A dopamine modified carbon felt (DPA/CF) electrode was located in the cathode chamber to produce H2O2 by the two-electron reduction of O-2 with electrons generated on the anodes. Under sunlight irradiation, the TNA photoanode initiated the degradation of perfluorodecylamine (PFDA) as typical refractory pollutant and selectively transformed its organic nitrogen to N-2 and NO3- with yields of 87% and 12%, respectively. Compared with PFDA removal efficiency using single flocculation, the efficiency was improved by more than 5 times (ca. 96.6%) in the combined process of photo-oxidation and flocculation center dot H2O2 production was also achieved using the DPA/CF cathode, obtaining a high concentration of 5.0 mM. Furthermore, this study revealed that the reversible reaction between dehydrogenation and hydrogenation on polydopamine accomplished the catalytic reduction of O(2)to H2O2. The present study proposes a new approach involving energy recovery in saline wastewater treatment for an energy-sustainable society.