© 2019 by the authors. Microwave (MW) heating of supported metal nanoparticles (NPs) presents attractive effects on catalysis such as the rapid heating processes and the enhancement of the reaction rate. Improving the heating property of the NPs, which act as the catalytic active sites, the MW effects will become more significant. Here we show a systematic study about the supported Pt NPs structure to improve the MW heating property. We found that the drastic heating was induced by a percolated Pt NPs structure, where the conduction electrons move around in the two-dimensional network. On the other hand, no heating was observed in an isolated Pt NPs system with the confined electrons. We conclude that the percolation of the Pt NPs giving the network structure is one of the important key factors for the efficient MW heating. The optimized Pt NPs catalyst leads to the dramatic MW effects on catalytic reactions.