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W/Zr based metallic glass composite is the novel generation of multifunctional energetic structural materials. The quasi-sealed chamber tests are applied in order to investigate the shock-induced reaction characteristics of porous W/Zr-based metallic glass composite at various impact velocities. The influences of the cover plate thickness on the overpressure are also tested. Thermochemical theory of temperature controlled shocked-induced chemical reactions is used to analyze the reaction characteristics of materials, as well as to identify the reaction parameters. The experimental and theoretical results show that the peak value of the quasi-static pressure and impact velocities of the fragments had positive correlation. The critical velocity to initiate the reaction is around 766 m/s. For certain velocity, there would be an optimal thickness of cover plate to maximize the overpressure behind the plate. However, the behind-plate overpressure effect is relatively mild while the cover plate thickness less than 8 mm. The critical shock pressure P_c to initiate the chemical reaction is 18.37 GPa. Relatively, the theoretical critical shock temperature T_c is calculated to be 3736.6 K. The theoretical results show that the reaction efficiency in the chamber are increased with increasing of shock pressure or temperature. The theoretical reaction efficiency reaches 61.5% when the shock pressure is 40 GPa. Therefore, the chemical reactions of the material are uncompleted in the experiments.