This paper attempts to disclose how temperature variation affects the electromagnetic shielding of a multilayer composite made of copper (Cu) fibers surrounded by silicon (Si). The model of the composite was fabricated by physical vapor deposition method, and tested with the temperature rising from room temperature (RT), 50º C, 85º C to 110º C. Under these temperatures, several electromagnetic shielding parameters of the composite were measured in various operating microwave frequencies (E, F, I and J bands). Among them, dielectric permittivity was acquired by LCR tester, magnetic permeability was measured by vibrating sample magnetometer (VSM), and the electromagnetic (EM) wave attenuation was recorded by typical microwave test bench. The results show that the composite had an EMI shielding of 20dB at 85º and 100dB at the RT; the reflection loss of the composite (volume fraction: 0.32) was also 100dB at the RT. Thus, the temperature rise suppresses the reflection loss; the composite has better electromagnetic shielding effect at the RT than at elevated temperatures; the volume faction enhances the wave attenuation of the composite. The results provide a good reference for the design of stable electromagnetic shielding materials at elevated temperatures.