The ultra-precision polishing assisted by the ultraviolet rays irradiation was performed to achieve the atomic-scale planarization of the single crystal diamond substrates. This polishing method is a novel and simple polishing method characterizing by a quartz disk and an ultraviolet irradiation device. The principle three crystal planes of the diamond substrate were polished by this method. The polished surfaces were evaluated by an optical interferometric profilers (Wyko), an atom force microscope (AFM) and LEED (low-energy electron diffraction). The surface roughness of the polished diamond substrates was evaluated as 0.2 ~ 0.4 nmRa in (100), (110) and (111) crystal planes. The LEED (low-energy electron diffraction) patterns indicated the almost perfect crystallographic structure without the residual processed strain beneath the polished surface. In this paper, the optimum polishing condition to achieve the atomic-scale planarization of the diamond substrates has been investigated by the evaluation of LEED patterns, Wyko and AFM images. The mechanismof the ultraviolet rays assisted polishing is discussed in detail.