The inherent periodic structure of montmorillonite limits the adsorption capacity of its endogenous active units such as Si-O tetrahedron and Al-O octahedron for pollutants. The high-intensity ultrasound method was used to release these active units and the layer-by-layer assembly was adopted to prepare carbon@chitosan@montmorillointe microsphere adsorbent (C@CS@Mt) to give full play to the adsorption capacity of montmorillonite. The montmorillonite nanosheet exhibited good hole-making ability, resulting in high surface area, pore volume and pore diameter of microspheres. Benefitting from the release of active sites in Si-O tetrahedron and Al-O octahedron of montmorillonite nanosheets, the adsorption capacity of C@CS@Mt was significantly improved. The maximum adsorption capacities of Pb2+ and methylene blue (MB) reached 884.19 mg·g-1 and 326.21 mg·g-1, respectively. The simultaneous adsorption experiments indicated that the occupation of active sites by Pb2+ caused the observed decrease of MB adsorption capacity. The theoretical calculations indicated that Pb was preferentially adsorbed by active adsorption units due to strong electron donating ability in comparison to MB. As an active unit, Si-O tetrahedron exhibited stronger adsorption capacity for cationic dyes than Al-O octahedron due to both the large electronegativity and lower adsorption binding energy.