Zeolite NaX@NaA core-shell microspheres were prepared via a post-treatment secondary growth of zeolite NaA films on outer surface of binderless zeolite NaX microspheres. The obtained core-shell microspheres were composed of intergrown octahedral NaX particles inside, with particles size of ca. 500–750 nm, and continuous zeolite NaA films on the outer surface with the thickness of about 2 μm. Higher CO2 separation performance was observed for the core-shell microspheres comparing to the parental binderless zeolite NaX microspheres. The ideal separation factors of zeolite NaX@NaA core-shell microspheres for CO2/CH4 and CO2/N2 were 13 and 47, and the adsorption selectivities for the corresponding binary mixtures were 308 and 923, significantly higher than the binderless zeolite NaX microspheres of 9 and 19 as well as 264 and 735, respectively. After K+ ion exchanging, the core-shell zeolite microspheres have even higher adsorption selectivities of 326 and 1109 for CO2/CH4 and CO2/N2 binary mixtures. The crushing strength of the binderless zeolite NaX microspheres was increased from 0.46 MPa to 3.42 MPa after the secondary growth. In addition, the growth of zeolite A film was resultant from interzeolite conversion and the interzeolite conversion was investigated by the conversion of zeolite NaX to NaA crystals in NaA membrane synthesis gel.