Abstract: In order to accurately measure the secondary electron yield (SEY) of the material at different incident electron energies and angles, and the energy spectrum of the secondary electrons, a measurement system with a spherical collector is built. First, the structure, measurement principle and neutralization method of the measurement system are introduced, and the obtained signal waveform is analyzed. Subsequently, the SEY and energy spectrum of Cu and Al2O3samples are measured. The measurement results show that the standard deviations of the SEY values measured at different incident energies are less than 0.055 (Cu) and 0.126 (Al2O3). The measured SEY values at different incident angles are in good agreement with the theoretical model, and the fitted R2 is 0.998 64 (Cu). Most of the emitted secondary electron energy is concentrated below 10eV(Cu) and 20eV (Al2O3), respectively, which is in line with the expectations of theory.