Microwave heating is a promising technique for heterogeneous catalytic reactions in plastic decomposition. The microwave-insensitive plastic material requires microwave-absorbing catalysts to facilitate catalytic-assisted decomposition and synergistic heating. However, the heating characteristics of catalyst particles within the microwave system is still unclear. In this study, the effects of particle size, particle arrangement direction, and particle shape on the microwave heating behavior of particles was investigated, and the model was experimentally validated and analyzed using infrared temperature data. The simulation results indicated that the heating rate increased as the particle size enlarged, with an average heating rate of 5.56 °C/s for the particle with a radius of 5 mm in comparison to 4.29 °C/s for that of 1 mm. Additionally, when particles were aligned parallel to the applied electric field, the electric field was intensely focused at the interparticle area, with a maximum electric field strength difference of 2.2 × 104 V/m in the samples. In contrast, the horizontal placement resulted in reduced electric field intensity (4.7 × 103 V/m) and lower temperatures (62 °C) near the areas adjacent to the particles compared to the maximum values in the particles. With respect to particle shape, cylindrical particles possessing larger aspect ratios exhibited superior heating performance due to the extended span of intraparticle microwave transmission aligned with the electric field direction but also resulted in increased thermal field distribution inhomogeneity. The research offers theoretical guidance to prevent catalyst sintering and promote microwave-assisted catalytic plastic decomposition.