Carbon dioxide‐enhanced water recovery (CO2‐EWR) is a promising strategy for managing reservoir pressure build‐up and mitigating the risk of fault activation resulting from CO2 injection in deep saline aquifers. CO2‐EWR can also be employed for supplying the required water for different applications after a treatment stage for the produced saline water. In this study, a brief review on CO2‐EWR technology and its necessities are first carried out. After that, the feasibilities, advantages, and challenges of various available treatment technologies that can potentially be used to treat high total dissolved solids (TDS) brine are comprehensively assessed. Based on comprehensive evaluation on technologies, a chain desalination process, consisting of pretreatment, main treatment, and post treatment, is proposed as a strategic path for the treatment of high TDS brine extracted from the Shenhua CCS site. It is concluded that coagulation‐flocculation and gravity filtration are needed as primary stages to remove suspended particles, while membrane distillation (MD) is selected as a suitable main treatment technology for high TDS Shenhua brine. Then, MD treatment is comprehensively discussed for a small‐scale treatment of extracted Shenhua brine assuming that the pretreated brine is free of suspended solids. After presenting the heat and mass transfer equations for direct contact membrane distillation (DCMD), a mathematical thermodynamic model is programmed in EES (Engineering Equation Solver) software to briefly analyze the performance parameters of DCMD. The results indicate that the designed DCMD, in the absence of auxiliary systems and considering the inherent temperature of extracted brine from different formations, has the capability of producing 15.1 kg m−2hr of freshwater from the extracted brine of the Shihezi formation layer. In the case of employing the auxiliary system of flat‐plate collector (FPC) combined with heat exchanger (HX) to heat up the extracted Shenhua brine to the desired temperature of 80°C, the amounts of produced flux are enhanced by 133%, 72%, and 45% for the brine extracted from Liujiagou, Shiqianfeng, and Shihezi formations, respectively. Using the yearly solar radiation model in TRNSYS software, the maximum solar radiation on the tilted surface at the location of Shenhua project in Inner Mongolia Autonomous Region of China reaches 3800 kJ m−2hr at 1 PM on April 1. Considering maximum solar radiation on the tilted surface, it is proved that a small‐surface FPC can supply the required energy to heat up the extracted brine from its inherent temperature to the desired temperature of 80°C. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.