Membrane capacitive deionization (MCDI) is an attractive desalination technique to achieve pure water by adsorbing ions in charge porous electrodes. In the current study nano-porous and micro porous activated carbon was derived from Limonia acidissima shells. The Limonia acidissima shell activated carbon (LASAC) prepared with chemical and thermal modification. The characterization techniques such as SEM, TGA, DTA, DTG, and N-2 adsorption desorption isotherm analysis were used for analysis LASAC. The LASAC electrode was used in MCDI lab scale self-made set up for simultaneous sorption of Cr(VI) and fluoride from the aqueous system. The LASAC electrode performance of was found effective for simultaneous removal of Cr(VI) and fluoride from mixed feed solution with maximum electrosorption capacity of Cr(VI) and fluoride were found to 0.8086 mg/g and 0.7805 mg/g for 10 mg/L; 3.227 mg/g and 2.7554 mg/g for 100 mg/L respectively. The parameters estimation of the monocomponent isotherm, multicomponent isotherm models and kinetic models were carried out in the present study. Thus MCDI with LASAC electrode could be useful for treatment of low concentrated Cr(VI) and fluoride wastewater.