Trifluoromethane (R-23), a ubiquitous byproduct of chlorodifluoromethane (R-22) synthesis, is one of the most potential greenhouse gases. The encouraged approach is thermal oxidation to process the vent gas by the clean development mechanism (CDM). Though such an approach could avoid the adverse environmental impacts, it will result in a great economic loss that includes not only the incineration cost but also the waste resource of R-23. R-23 is valuable as a refrigerant, fire suppression agent, and plasma etchant (purity: 99.999 mol %). In this work, the distillation-pressure swing adsorption (DIST-PSA) process was employed to concentrate R-23 from 88% to 99.999% in the vent gas economically. Dynamic breakthrough experiments were performed to predict the adsorbent separation performance. Results indicated the coconut activated carbon (SAC-1) is appropriate material for R-23 and R-22 separation. The SAC-1 has a high separation factor value for R-22 and R-23 under the experimental conditions. Afterward, the DIST-PSA hybrid system was studied by process simulation and their energy consumption was analyzed. According to the comprehensive analysis, the best performance is obtained with a feed composition of 88% R-23/12% R-22 for the PSA unit. Process simulation predicts R-23 recovery, purity, and energy consumption, respectively, of 69.52%, 99.9993% and 99.59 kJ.kg(-1) R-23. Overall, our studies have revealed that coupling a PSA unit with distillation is a feasible and promising technique to separate high purity R-23 efficiently and economically in the R-22 synthesis industries.