Solar‐driven interfacial evaporation (SDIE) has played a pivotal role in optimizing water‐energy utilization, reducing conventional power costs, and mitigating environmental impacts. The increasing emphasis on the synergistic co‐generation of water and green electricity through SDIE is particularly noteworthy. However, there is a gap of existing reviews that have specifically focused on the mechanistic understanding of green power from WEC systems, the structure‐activity relationship between efficiency of green energy utilization in WEC and materials design in SDIE. Particularly it lacks a comprehensive discussion to address the challenges faced in these areas along with potential solutions. Therefore, this review aims to comprehensively assess the progress and future perspective of green electricity from water‐electricity co‐generation (WEC) systems by investigating the potential expansion of SDIE. Firstly, it provides a comprehensive overview about materials rational design, thermal management and water transportation tunnels in SDIE. Then it summarizes diverse energy sources utilized in the SDIE process, including steaming generation, photovoltaics, salinity gradients effect, temperature gradients effect, and piezoelectric effect. Subsequently, it explores factors that affect generated green electricity efficiency in WEC. Lastly, this review proposes challenges and possible solution in the development of WEC. The timely emergence of this review will promote the sustainable use of energy.This article is protected by copyright. All rights reserved