High energy particle bombardment of silicon carbide can lead to the accumulation of defects and lattice disorder, which can negatively affect physical property and reduce lifetime of SiC devices. Thus, it is essential to systematically study the damage of SiC in different radiation environment. Herein, 6H-SiC was irradiated by neutrons at the fluence of 5.74×10¹⁸, 1.74×10¹⁹, 2.58×10²⁰ and 1.27×10²¹ n/cm², and then annealed. Changes in lattice parameters from post-irradiation isochronal annealing for 30 min in the range of 500-1650 ℃ were measured using X-ray single crystal diffraction. The results showed that the lattice swelling and recovery behavior were isotropic. Based on the swelling data, it was concluded that the neutron irradiation-induced defects in 6H-SiC were primarity point defects. Both intrinsic and irradiation defects can introduce defect energy levels, which were mainly caused by vacancies and led to the absorption band edge redshift and band gap narrowing of SiC. The defect energy levels of these vacancies and vacancy-associated defects were determined by absorption spectra, luminescence spectra and Raman spectra. Experiments and first principles calculation showed that the silicon vacancies introduced defect levels above the valence band, while the carbon vacancies introduced levels below the conduction band. The infrared absorption at 1382 nm and 1685 nm and the emission at 550 nm of unirradiated 6H-SiC were mainly due to the intrinsic carbon vacancies. The luminescence of post-irradiated SiC at 415, 440 and 470 nm was mainly due to the silicon vacancy produced by irradiation and its related defect configuration. All above data revealed the luminescence mechanism of SiC based on the charge state and the defect energy level distribution.