The extensive usage of fossil fuels associated with the huge emission of greenhouse gases accelerates the global warming effect and its associated climate change phenomena. Natural gas (CH₄) is considered as an environmentally friendly combustion fuel and is a good alternative to alleviate this phenomenon. However, the natural gas streams contain huge concentrations of CO₂ creating corrosion and combustion quality demerits for using of natural gas directly. Therefore, the selective capture of CO₂ from natural gas streams via an energy-efficient adsorption process in porous materials is a mandatory industrial requirement before the distribution and commercialization of CH₄.  In this review, a brief review of porous materials, classification, synthesis, and exploitation of porous materials in natural gas purification was studied. Moreover, recent advances in the separation selectivity of CO₂/CH₄ and its separation adsorption action were briefly discussed.