In the present study, the effect of 2, 2`-Azobis (2-methylpropionamidine) dihydrochloride (AIBA) on the abrasive-free polishing (AFP) of hard disk substrate was investigated. Polishing experiment results indicate that the material removal rate (MRR) of hard disk substrate polished in slurry containing AIBA and peroxyacetic acid (PAA) is obviously higher than that without AIBA. Furthermore, the acting mechanism of AIBA in AFP of hard disk substrate was analyzed. Auger electron spectrometer results demonstrate that the oxidation reaction occurred on the surface and formed a passivation layer. The potentiodynamic polarization tests show that AIBA can increase the corrosion rate of the hard disk substrate in PAA-based slurry, and accelerate the dissolution reaction of oxidation film, which lead to the improved MRR in AFP process.