As predicted by the International Energy Agency, our planet faces an energy and water crisis in the next 20 years. [1] Human demand for energy and water continues to increase, but the amounts produced are insufficient to meet consumption. [2][3][4][5][6] The ocean is a huge water source, and freshwater can be obtained by salt removal from seawater, which can be performed via two major commercial techniques: thermal distillation and membrane processing. [7][8][9][10][11][12][13][14] The thermal-based desalination techniques include multi-stage distillation, multieffect distillation, and vapor compression, all of which consume tremendous amounts of thermal energy. For example, the total energy consumption of a multistage flash evaporation process is in the range of 50-100 kWh m −3 to achieve highquality water production. [8,15] This makes it only suitable for specific areas with abundant thermal energy sources. Membrane-based desalination includes reverse osmosis and electrodialysis processes. [11,[16][17][18] Using these techniques can reduce energy consumption to <10 kWh m −3 with an output water quality with a salt content of <500 ppm. [8,19,20] In this regard, special attention has been paid to energy and water demand by the research community. [21][22][23][24] These issues have led to the development of a new technique in which renewable energy and desalination technologies are externally coupled to minimize energy consumption. [25] In contrast to the above techniques, electrochemical desalination has become a promising and versatile method that offers dual roles of desalination and energy storage simultaneously. [26][27][28][29][30][31][32][33][34] It removes salt ions through electrode-based reactions either by physical adsorption (capacitive deionization or nonfaradaic processes) or chemical reaction processes (battery desalination or faradaic processes). Meanwhile, the photoelectrochemical process technology becomes a crucial part for the environmental remediation, for instance: the process of water splitting by photoelectrochemical method paves a new way to reduce energy consumption. [35][36][37] Similarly, to achieve a zero-energy consumption process, photoelectrochemical desalination technology has recently been introduced. [38,39] In addition, another concept of solar desalination has been extensively studied: solar thermal desalination. In solar thermal Solar-assisted electrochemical desalination has offered a new energy-water nexus technology for sustainable development in recent studies. However, only a few reports have demonstrated insufficient photocurrent, a low salt removal rate, and poor stability. In this study, a high-quality freshwater level of 5-10 ppm (from an initial feed of 10 000 ppm), an enhanced salt removal rate (217.8 µg cm −2 min −1 of NaCl), and improved cycling and long-term stability are achieved by integrating dye-sensitized solar cells (DSSCs) and redox-flow desalination (RFD) under light irradiation without additional electrical energy consumption. The DSSC redox electrolyte ...