We present a comprehensive experimental and simulation study on a low-cost and efficient CO2 capture technique using nanostructured zeolite NaX in a vacuum pressure swing adsorption (VPSA) process. The nanostructured zeolite NaX adsorbent has a high CO2 adsorption capacity, a relatively high adsorption and desorption rate, and a large CO2 selectivity over N-2. Therefore, it is suitable for post combustion CO2 capture from dry flue gas. A series of nanostructured zeolite NaX pellets are prepared with different ratios of binder material and at different sintering temperatures. The results from mechanical properties, adsorption isotherms, kinetics and breakthrough experiments demonstrate that nanostructured zeolite material prepared with a low ratio of binder that sintered at 500 degrees C has the best separation performance for a CO2/N-2 mixture. In addition, the results indicate that the nanostructured zeolite NaX samples lead to a better separation performance compared with the commercial microsized zeolite NaX. Process optimization studies employing the above adsorbents were performed to minimize the energy consumption of the process for a specified product purity and recovery rate. The decision variables include the feed pressure, blowdown pressure, evacuation pressure, feed flow rate, and length to diameter ratio of the adsorption bed. The effect of cycle time was investigated independently due to the need for synchronization of the multi-bed configuration. The optimization results indicate that the energy consumption of the process with nanostructured zeolite is about 30% lower while achieving a higher CO2 purity and productivity compared with a process employing a commercial microsized zeolite.