Reinforced polymer blend is a well-practiced area of interest adopted by materials scientist throughout the world due to its tunable end properties. The present study has been fueled by developing an immiscible thermoplastic elastomeric blend (polystyrene/ethylene-co- methyl acrylate copolymer) with loading of conducting carbon black (Vulcan XC 72); an overworked conductive clustered carbon filler. The work emphasized selective dispersion of carbon particulates in one phase (ethylene-co-methyl acrylate copolymer) resulting lowering of electrical percolation and excellent EMI shielding effectiveness in low loading. The conductive blend was also cross-checked to establish their superiority in physico-mechanical, rheological behaviors and thermal stability. The microscopic analysis has implied dispersed islands of clustered carbon particles inside blend ensuing path for electronic hopping. The segregated microstructure also has been correlated to their frequency dependent conductivity, skin depth analysis and EMI shielding measurement.