Aspheric thin-walled crucibles with large diameters are widely used for photovoltaics and semiconductor industries, while they have hard-brittle and aspheric characteristics. Nevertheless, these crucibles strictly require atomic surfaces and high material removal rate (MRR). This is a challenge for chemical mechanical polishing (CMP). To break this challenge, a novel green CMP was developed for fused silica, containing ceria, lanthana, hydrogen peroxide, diethylene triaminepentaacetic acid pentasodium, carboxymethyl cellulose sodium and guanidine carbonate. After CMP, surface roughness Ra of 0.115 is obtained at a scanning area of 5 × 5 μm2 measured by atomic force microscopy, and MRR is 563 nm/min. In such an atomic surface, the MRR is the highest compared with those published previously. Transmission electron microscopy confirms that the thickness of damaged layer after CMP is only 2.63 nm. A novel approach of robot floating polishing is proposed for aspheric crucibles with a diameter of 810 mm and a height of 580 mm. Using the developed CMP, surface roughness Sa of 0.178 nm on inner surface of an aspheric thin-walled crucible is achieved under a measurement area of 50 × 50 μm2. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance reveal that the content of Ce3+ increased from 28.54 to 43.76 %. Through Raman, XPS and Fourier transform infrared spectroscopy, CMP mechanisms are elucidated. Densified damaged layer on the surface of fused silica was induced by the transformation of surface structure from six-membered to four- or three-membered network. Ce-OH and Si-OH were formed between fused silica and ceria abrasives, forming Ce-O-Si by condensation reaction of dehydration. The developed green CMP and approach provide new pathway to polish and manufacture atomic surfaces for aspheric thin-walled crucibles with large diameters.