X-ray communication technology is a kind of space communication mode using X-ray as a carrier, which has the advantages of a large communication bandwidth, light weight, small volume, low power consumption, and high confidentiality. By designing a multi-target X-ray signal modulation device, the X-ray communication rate can be improved, and the accuracy of X-ray energy spectrum recognition at the signal receiving end can be ensured, so that the advantages of X-ray communication based on energy load can be truly played. In this paper, an X-ray communication demodulation method based on peaking multi-level support vector machine is proposed to accurately identify the X-ray characteristic energy spectrum of multi-target materials. A peaking multi-level support vector machine classifier suitable for four-element communication is designed. The parameter tuning and verification ensure high accuracy and generalization ability. The simulation results show that support vector machine provides an efficient, accurate, and robust signal recognition solution for X-ray communication based on energy load.