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The discharge caused by metals triggered by microwave radiation is a key issue, whereas little attention was paid to the pyrolysis of waste tires by using the interaction between microwave and metals. In this work, the effect of such factors, that is, the microwave power, the steel wire (SW) mass fraction, and its spatial position in the tire powders (TPs), as well as the flow rate of the carrier gas, on the pyrolysis of the samples were experimentally examined in a laboratory-scale microwave oven. It was observed that the addition of SWs significantly accelerated the pyrolytic reaction of the TPs with regard to the conversion rate (product yields), even at rather low power, which may lead to a more complete degradation and significant reduction in the economic cost of the process. In addition, the presence of SWs has significant effects on the composition of products with different phases, especially gas yield (up to 35.3%) and also the H2 concentration in tires (up to 16.11%) were extremely high. The research on the discharge triggered by metals subjected to microwave irradiation will be instructive for promoting the industrial applications of discharges due to microwave radiation.