A novel solar‐assisted cascade Rankine cycle‐driven reverse osmosis (RO) system is proposed and evaluated using conventional and advanced exergy analysis. The system comprises a solar collector as a heat input, steam Rankine cycle (SRC), and organic Rankine cycle (ORC) to generate turbine work and RO units for brackish water treatment. Water and R1233zd(E) are used as the working fluid in the SRC and ORC, respectively. The RO system is proposed to produce 1 m3 h−1 of permeate water from each RO unit. Conventional exergy analysis shows that the solar collector exhibits the highest exergy destruction of 0.798 kW, followed by the RO unit. However, advanced exergy analysis reveals that only 16.16% of the avoidable exergy in solar collectors can be reduced due to technical constraints. Advanced exergy analysis identified that endogenous avoidable exergy destruction contributes 24% of overall exergy destruction, which can be reduced by optimizing operating parameters and making technical improvements. The RO unit has a higher exogenous avoidable exergy, potentially suggesting improvements in other system component parameters. The advanced exergy analysis also prioritized the components for improving system performance in a sequence of RO high‐pressure pumps, RO modules, solar collector, ORC condenser, evaporative condenser, ORC expander, and SRC turbine.