Petrochemical produced water (PPW) in oil and gas field consists a high concentration of pollutions and the largest wastewater streams. Current treatment technologies for PPW are highly expensive and limited to use. However, there is an urgent need to sustainable technology to treat this water. Microbial desalination cell (MDC) is consider as a costeffective and eco-friendly substitution to the currently available desalination and wastewater treatment methods. MDC endures from small desalination cell, low mass desalination rate and high internal resistance. Though, quadruple microbial desalination cell (QMDC) is a novel desalination configuration that has capability to generate high current and treat high saline water. Moreover, a novel design of QMDC is proposed with a large volume single desalination chamber in the middle of the system with multiple IEM's and surrounds by two anode and two cathode chambers on the sides to enhance electrical-gradient forces as per the system configuration and to reduce the internal resistance over the operation. The research aims to investigate QMDC performance using NaCl/PPW in term of current generation, power recovery and desalination rate. In the first stage, 35g/L NaCl was treated in QMDC using three connection modes (individual, parallel and series). As results, PQMDC showed the highest average current and power density (16.55 mA and 2.68 W/m2 respectively). Whereas the IQMDC generated the lowest average current (6.62 mA). Also, the findings indicated that the connection modes of QMDC were extremely sensitive to the system's internal resistance. The lowest internal resistance was in PQMDC (29.5Ω) in comparison with individual and series connections. Moreover, parallel connection revealed a high desalination rate of up to 45.89 mg/hr. PQMDC selected as the best connection modes to operate QMDC with high salinity PPW. However, the results of PQMDC using PPW as salt solution showed a high current generation (45.74 mA), maximum power density of 2.12 W/m2 and low internal resistance (25 Ω) with 5.6 g/L.d of concentration desalination rate in batch operation. However, more feasibility studies required to be conducted for determining the suitability of QMDC operation for real-scale operation and byproducts recoveries.