Many regions around the world have limited access to clean water and power. Low-grade thermal energy in the form of industrial waste heat or non-concentrating solar thermal energy is an underutilized resource and can be used for water desalination and power generation. This paper experimentally and theoretically examines a thermoelectric-based simultaneous power generation and desalination system that can utilize low-grade thermal energy. The paper presents concept design and the theoretical analysis of the proposed system followed by experimental analysis and comparison with the theoretical estimations. Experiments were carried out at three heat loads 50, 100 and 150 W to achieve varying temperature gradients across thermoelectric generators. During the experiments, thermoelectric generators were maintained at a hot to cold side temperature difference between 20 to 60 °C. The experiments showed that the power generation flux and freshwater mass flux increased with the increase in the thermal energy source temperature. The power flux varied between 12 to 117 W/m2 of thermoelectric generator area, while freshwater mass flux varied between 4.8 to 23.7 kg/m2⋅h. The specific thermal energy consumption varied between 3.6 to 5.7 MJ/kg of freshwater; this is comparable to the single-stage conventional distillation system.