This paper describes the basic principle of multiple diffraction, including diffraction indexing and its intensity calculation, as well as the direction determination of the incident X-ray that meets the Bragg condition for two specific crystal planes. It proposes a X-ray energy calibration method based on the crystal multiple diffraction. In theory, this calibration method can reach a very high precision of 1 eV when the scanning step is 1″. To verify the feasibility of this method, a test is performed on the 14B diffraction beam line of Shanghai source,and the 180° Φ scanning diffraction pattern for the silicon(111) is collected at 10 keV. All the possible diffraction planes are set up and the glitch is indexed according to the angle difference of them. After indexing of the glitch, the calibrated energy of 10.06 keV is obtained. The experimental results are consistent with the theoretical results well, which proves that the calibration method can achieve a high precise calibration for photon energies when the angle scanning accuracy meets the needs of experiments.