A thermoelectric distillation system has recently been demonstrated to have a great potential of improving the efficiency of distillation processes due to the use of waste heat from the hot side of thermoelectric module to assist evaporation while the cold side for condensation. This work investigates the key factors that affect the water production in a thermoelectric distillation system. An experimental investigation was performed to investigate the influence of evaporation temperature, vapour volume, Peltier current and input power on the water production rate. The results of the experiment show that an increase in the sample water temperature from 30 °C to 60 °C led to an increase in total water production by 47%. In addition, an increase in total water production by 58% was obtained by reducing the vapour volume from 600 cm3 to 400 cm3 during a 3-h operation. The maximum water production rate is achieved by appropriate selection and control of the Peltier current to the thermoelectric device based on the operating condition of the distillation system.