An analysis is reported of a geothermal-based electricity-freshwater system in which an organic Rankine cycle is integrated with a multi-effect distillation desalination unit. The system is driven by geothermal hot water extracted from the production well. Mass, energy, entropy, and exergy rate balances are written for all system components, as are energy and exergy efficiency expressions for each subsystem. The exergy destruction rate associated with the temperature and chemical disequilibrium of the freshwater and brine with the reference environment are taken into account to reveal accurate results for irreversibility sources within the desalination process. The developed thermodynamic model is simulated using thermodynamic properties of the working fluids (i.e., ammonia, seawater, distillate, and brine) at each state point. A sustainability analysis is performed that connects exergy and environmental impact concepts. That assessment expresses the extent of the contribution of the system to sustainable development and reduced environmental impact, using exergy methods. Results of the sustainability analysis indicate that, with an increase in the reference environment temperature from 20 to 35 $$^\circ{\rm C}$$
∘
C
, the exergy destruction rate decreases for the multi-effect distillation and organic Rankine cycle systems respectively from 6474 to 4217 kW and from 16,270 to 13,459 kW. Also, the corresponding sustainability index for the multi-effect distillation and organic Rankine cycle systems increases from 1.16 to 1.2 and 1.5–1.6, respectively, for the same increase in reference environment temperature.