Adsorption is the most promising technology used in the gas separation and purification process. The key success of this technology relies on the selection of an adsorbent. Activated carbon and zeolites are the most commonly used adsorbents in the separation of particular gas from gaseous mixtures. Activated carbon deriving from fossil and biomass-based resources has wide pore size distribution and thereby results in lower selectivity. Whereas, zeolites synthesized from natural minerals are expensive which increases the cost of the purification process. Taking this into concern, the quest for synthesizing low-cost and effective adsorbents has gained greater attention in recent years. Carbon Molecular Sieves (CMSs), are considered as an attractive alternative to replace the conventional adsorbents. Furthermore, CMSs exhibit higher selectivity and adsorption capacity, due to their narrow micropore size distribution (0.3–0.5 nm). CMSs are synthesized from any organic carbonaceous precursor with low inorganic content. Since most of the agricultural residues fall under this category, they can be used as a feedstock for CMSs production. The synthesis of CMSs involves three stages: carbonization, activation, and pore modification. In this review, physicochemical characteristics of various agricultural residues, the effects of carbonization process parameters, activation methods, and pore modification techniques adopted for producing CMSs are comprehensively discussed. The effect of deposition temperature, time, and flow rate of depositing agent on pore characteristics of CMSs is briefed. The prospects and challenges in CMSs production are also studied. The insights in this review provide guidelines for synthesizing CMSs from agro-residues. •Status of research on Carbon Molecular Sieves (CMSs) production is reviewed.•Agricultural residues are an excellent precursor for CMS production.•Chemical activation enhances porosity of activated carbon than physical activation.•CMSs exhibit higher selectivity and adsorption capacity than activated carbon.