During the production process of lead and zinc smelting, a highly hazardous solid waste is generated. This waste contains valuable metal resources such as mercury, selenium, and lead. Specifically, the waste contains high levels of mercury, making it a hazardous waste. Currently, the treatment processes for this mercury-containing solid waste have drawbacks, including the need for high temperatures and long heating times. A novel process using microwave external field enhancement for the removal of mercury was proposed. The study also determined the optimal process parameters and investigated the kinetics of mercury metabolism. The experimental results indicated that the mercury-containing group members were the main substances absorbing microwaves in the mercury-containing solid waste. In terms of optimal process parameters, a heating temperature of 600 °C, a reaction time of 30 min, an oxygen flow rate of 20 L/h, and a volatilization efficiency of mercury exceeding 99 % were achieved. The volatilization kinetics of mercury during heating of the mercury-containing solid waste followed a first-order reaction model. Furthermore, the activation energy for microwave mercury removal was found to be 6.06 kJ/mol lower than that for conventional mercury removal, with a value of 29.41 kJ/mol. This lower activation energy facilitated a higher mercury removal efficiency compared to conventional methods. The use of microwaves allows for the selective heating of the mercury-containing components in solid waste, resulting in an increased volatilization efficiency of mercury. By utilizing a microwave heating system, mercury is effectively recycled as high-mercury slag. This approach effectively addresses the environmental concerns associated with mercury-containing solid waste.