Composites made up of microparticles embedded in a polymeric matrix have attracted increasing attention due to the possibility of tailoring their physical properties by adding the adequate quantity of fillers. As the concentration of these fillers increases, their connectivity changes drastically at a given threshold and therefore the electrical, thermal and optical properties of these composites are expected to exhibit a percolation effect. In this work, the thermal and electrical conductivities along with the emissivity of composites composed of carbonyl-iron microparticles randomly distributed in a polyester resin matrix are measured, for volume fractions ranging from 0 to 0.55. It is shown that both the thermal and electrical conductivities increase with the particles’ concentration, such that their percolation threshold appears at volume fractions of 0.46 and 0.38, respectively. The emissivity, on the other hand, decreases as the fillers’ concentration increases, such that it exhibits a substantial decay at a volume fraction of 0.41. The percolation threshold of the emissivity is thus higher than that of the thermal conductivity, but lower than the electrical conductivity one. This dispersion on the percolation concentration is justified by the different physical mechanisms required to activate the electrical, thermal, and optical responses of the considered composites. The obtained results thus show that the percolation phenomenon can efficiently be used to enhance or reduce the physical properties of particulate composites.