Microwave heating provides a cleaner pyrometallurgical method for separating zinc from electric arc furnace dust (EAFD, a solid waste generated during steel production with excellent dielectric properties). Despite its undisputed heating efficiency, the impact of microwave heating characteristics on the zinc removal process from EAFD remains unclear. This paper focuses on ZnO, one of the primary components of EAFD, and develops an electromagnetic-thermal-chemical reaction model to analyze the effects of microwave power and graphite addition on heating behavior, reduction reactions, field distributions, and reaction kinetics. The results indicate that the heat generated from the interaction between microwaves and materials exhibits inherent non-uniformity, leading to the localized thermal effect and making the error of general temperature measurement methods. Increasing microwave power and adding graphite enhance heating efficiency and promote the reduction reaction but also result in significant internal-external temperature disparity and worse temperature distribution. At 1000 W, with 1.2 times the stoichiometric amount of graphite addition, the temperature measurement error reaches approximately 200 °C, potentially affecting the kinetic results to a certain degree. The non-isothermal kinetics results from simulations indicate that the localized thermal region exhibits a lower average activation energy of 47.5 kJ/mol compared to experimental results, suggesting that the lower activation energy of the ZnO reduction reaction during microwave heating is primarily caused by the localized thermal effect rather than the non-thermal effect. Additionally, in the energy distribution, the higher proportion of return loss during heating underscores the importance of a well-designed microwave heating system.