The experiments of the adsorption removal of CS2 impurity from a mimetic coke oven gas were performed by using a series of Na-type zeolites as adsorbents. Combining with the diffusion & simulation calculations and several characterizations, it's found both the development degree and the diffusion ability of microporous systems significantly influence the adsorption performance of these Na-type zeolites on which the physical absorption was predominant for CS2 molecules. Firstly, compared with NaZSM-5 or NaSAPO-34, the NaY with FAU-type framework exhibited a much higher breakthrough adsorption capacity, primarily due to its much higher microporous surface area & volume and larger-size channels, which ensured a broader adsorption space, a high-efficiency molecule-diffusion and a high adsorption utilization of micropores. Secondly, alkali-treatment introduced some mesopores into NaZSM-5 crystals but also resulted in a declined integrity of microporous structure, causing an obvious decline of adsorption performance. Thirdly, the nano-crystal NaZSM-5 or NaY exhibited a much higher breakthrough adsorption capacity than that of the corresponding micron-crystal zeolite, primarily attributed to both the increased microporous surface area & volume and the shortened micropore diffusion-path length of the former. In addition, a breakthrough adsorption capacity of up to 0.251 g/g was obtained in the first adsorption use of a nano-NaY-0.909 sample at 298 K, and it's 0.229 g/g in even the sixteenth time of operation (by then, total adsorption service hours were 80.58 h). Our work may provide an important reference for developing high-performance adsorbents for removing gaseous CS2 impurity in coke oven gas.