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Silicon carbide (SiC) is widely used in many research fields because of its excellent properties. The femtosecond laser has been proven to be an effective method for achieving high-quality and high-efficiency SiC micromachining. In this article, the ablation mechanism irradiated on different surfaces of 6H-SiC by a single pulse under different energies was investigated. The changes in material elements and the geometric spatial distribution of the ablation pit were analyzed using micro-Raman spectroscopy, Energy Dispersive Spectrum (EDS), and an optical microscope, respectively. Moreover, the thresholds for structural transformation and modification zones of 6H-SiC on different surfaces were calculated based on the diameter of the ablation pits created by a femtosecond laser at different single-pulse energies. Experimental results show that the transformation thresholds of the Si surface and the C surface are 5.60 J/cm2 and 6.40 J/cm2, corresponding to the modification thresholds of 2.26 J/cm2 and 2.42 J/cm2, respectively. The Raman and EDS results reveal that there are no phase transformations or material changes on different surfaces of 6H-SiC at low energy, however, decomposition and oxidation occur and then accumulate into dense new phase material under high-energy laser irradiation. We found that the distribution of structural phase transformation is uneven from the center of the spot to the edge. The content of this research reveals the internal evolution mechanism of high-quality laser processing of hard material 6H-SiC. We expect that this research will contribute to the further development of SiC-based MEMS devices. [ABSTRACT FROM AUTHOR]