Zirconia ceramics are the promising materials for cell phone backplanes in the 5G era, and smoother surfaces and higher removal efficiency are sought after for their precision machining. Although nanodiamond abrasives have high polishing rates, it is easy to bring mechanical scratches and pits on the ceramic surface because of their high hardness, resulting in degradation of the surface quality of the finished workpiece. Therefore, polyacrylamide grafted nanodiamond particles were prepared by solution polymerization method for polishing ceramic wafers. As confirmed by Fourier transform infrared spectroscopy (FTIR), the polyacrylamide has been grafted on the nanodiamond surface. According to the scanning electron microscopy (SEM) and particle size distribution, the composite abrasives have better dispersion than pure nanodiamond abrasives. The results of chemical mechanical polishing (CMP) experiments showed that the composite abrasives could reduce the average surface roughness (Sa, arithmetic mean height) of zirconia ceramic from 28.31 nm to 2.68 nm (scanning area is 500 μm × 500 μm), and the polishing rate remained high compared to pure nanodiamond abrasives, showing superior CMP performance. X-ray photoelectron spectroscopy (XPS) demonstrated that solid-phase chemical reactions occurred during the polishing process to form ZrSiO4. Meanwhile, contact-wear model combined with contact angle testing indicates that the introduction of polyacrylamide increases the contact area of the nanodiamond on the zirconia wafer surface, thereby significantly enhanced the mechanical effect.