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A solvothermal reaction of anhydrous C3N3Cl3 and Li3N using benzene as the solvent has been carried out to prepare crystalline carbon nitrides successfully at 350℃ and 5-6 MPa. X-ray diffraction (XRD) indicated that the major part of our brown sample was mainly composed of α-C3N4 and β-C3N4 with lattice parameters of a = 0. 65 nm, c = 0.47 nm for α-C3N4 and a = 0.644 nm, c = 0. 246 nm for β-C3N4, which match the latest ab-initio calculations quite well. The N/C ratio in the powder is about 0.66. The Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses suggested the presence of both single and double carbon-nitrogen bonds. The kinetics effects of our solvothermal reaction to prepare crystalline carbon nitrides are also discussed chiefly.