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Herein, we reported on the study of percolation dynamics in thermoset-based die attach (DA) materials and its effect on percolation conductivity. Two types of percolation mechanism in thermoset based DA were discovered, i.e., the curing reaction-induced percolation and the physical aging-induced percolation. The former features in a fast percolation network growth rate, which is one order of magnitude higher than the latter. It is demonstrated that the percolation kinetics largely affects the apparent percolation conductivity under the traditional packaging conditions; and reaction-induced percolation allows ultrahigh efficiency in reaching the volume fraction-limiting percolation conductance, resulting in enhanced thermal performance of DA.