Capacitive deionization (CDI) has been considered a reliable technology used to provide water with low salt concentration and low energy consumption. However, there are still some drawbacks to overcome concerning the choice of the electrode material. Carbon electrodes are extensively used for CDI electrodes since they provide a stable material with high pore volume and good conductivity. However, it is been challenging to find a low-cost symmetric CDI electrode with high salt adsorption capacity (SAC), fast electrosorption kinetics and good energy efficiency. Recently, our group published a paper reporting the use of activated carbon derived from polyaniline (PAC), a low-cost precursor, with high SAC and good electrosorption kinetics. It was demonstrated that the use of different polyaniline (PAni) dopants have a strong influence on the activate carbon properties and, consequently, the electrode performance for CDI. In the present research, it was explored the use of PAC electrodes varying the carbonization temperature before the activation. It was observed a strong dependence of the specific surface area (SSA) and pore size distribution (PSD) on the carbonization temperature. When low temperatures (500 °C) were employed during carbonization (PAC500), the BET SSA was 3653 m²/g and pore volume of 2.50 cm³/g was obtained while at higher carbonization temperatures (850 °C) this value was much lower (2362 m²/g of SSA and 1.26 cm²/g of pore volume for PAC850). The BET SSA obtained in this work is among the highest values reported in literature. The explanation for this high value is probably ascribed to the reactivity of the low temperature carbonized PAni with KOH. Indeed, when PAni was carbonized in temperatures lower than 500 °C all the material was consumed during the activation step, indicating a strong reactivity of the precursor with KOH. These values of SSA and pore volume resulted in an outstanding performance as symmetrical electrodes for CDI. The capacitance of PAC500 and PAC850 measured in a NaCl 0.2 M solution were 213 F/g and 162 F/g, respectively. These impressive values are result of the high SSA and pore volume of PAC materials. Finally, the CDI desalination carried out in batch operation mode also showed an outstanding SAC performance for symmetric electrodes, achieving 22 mg/g for PAC500 and 15 mg/g for PAC850. Moreover, 85% and 76% of electrode saturation was reached after 5 minutes of electrosorption for PAC500 and PAC850, respectively, indicating very fast electrosorption kinetics. This work present a very promising electrode material for CDI and shows how important is the carbonization temperature for PAC electrodes.