Abrasive is the one of key influencing factors during chemical mechanical polishing(CMP) process. Currently, α-Alumina (α-Al2O3) particle, as a kind of abrasive, has been widely used in CMP slurries, but their high hardness and poor dispersion stability often lead to more surface defects. After being polished with composite particles, the surface defects of work pieces decrease obviously. So the composite particles as abrasives in slurry have been paid more attention. In order to reduce defect caused by pure α-Al2O3 abrasive, α-alumina-g-polystyrene sulfonic acid (α-Al2O3-g-PSS) composite abrasive was prepared by surface graft polymerization. The composition, structure and morphology of the product were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), time-of-flight secondary ion mass spectroscopy(TOF-SIMS), and scanning electron microscopy(SEM), respectively. The results show that polystyrene sulfonic acid grafts onto α-Al2O3, and has well dispersibility. Then, the chemical mechanical polishing performances of the composite abrasive on glass substrate were investigated with a SPEEDFAM-16B-4M CMP machine. Atomic force microscopy(AFM) images indicate that the average roughness of the polished glass substrate surface can be decreased from 0.835 nm for pure α-Al2O3 abrasive to 0.583 nm for prepared α-Al2O3-g-PSS core-shell abrasive. The research provides a new and effect way to improve the surface qualities during CMP.