As the global photovoltaic industry expands, the production of solar cells generates significant quantities of wastewater, characterized by high concentrations of ammonia-nitrogen and fluorine. To sustainably manage this wastewater, it is crucial to evaluate and optimize existing treatment systems. In this study, three innovative photovoltaic wastewater treatment routes that integrate resource utilization processes are proposed. A comparative assessment of the sustainability performance of these three routes, alongside a conventional treatment route, was conducted using pilot-scale data. The findings reveal that recycling cryolite and ammonium chloride is the most environmentally friendly approach, whereas recycling fluorspar and ammonium chloride proves to be the most economically feasible. Chemical usage emerges as the predominant contributor to nearly all environmental impacts, although the recovery of high-value components offers certain benefits. Among the resource products recovered, cryolite yields the highest environmental benefits, followed by ammonium chloride, with fluorspar providing the least. Furthermore, the adoption of alternative green chemicals, precise control of chemical dosages, and maximization of energy efficiency are identified as key strategies for reducing both the environmental burden and economic costs. In conclusion, this study quantitatively evaluated the potential environmental impacts and economic benefits of a conventional treatment method and three novel resource utilization approaches, thereby providing a scientific foundation for the improvement and selection of wastewater treatment technologies in the photovoltaic industry.