Sodium alginate/Na+-rectorite (SA/Na+REC) intercalated nano-composite microspheres were prepared in an inverse suspension system. The effect of the preparation conditions of SA/Na+REC composite microspheres on adsorption capacity for Basic Blue 9 was investigated. The structure and morphology were analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the optimal condition was that the amount of Na+-rectorite was 2wt%, the amount of cross-linker was 0.384% and the amount of the initiator was 8%. SEM showed that it is porous products with spherical particulate surface. XRD showed that intercalation is formed between Na+-rectorite and sodium alginate. The adsorption capacity of SA/Na+ REC was investigated in comparison with Na+-rectorite and sodium alginate using different cationic dyes. The SA/Na+REC composite microspheres showed the highest adsorption capacity. The reason lies in the existence of intercalated sodium alginate. It could enlarge the pore structure of microspheres, facilitating the penetration of macromolecular dyes.