Tri-continuous structure poly(vinylidene fluoride)/polystyrene/high density polyethylene (PVDF/PS/HDPE) ternary blends was fabricated as a candidate for structuring high electrical performance composites. By adding MWCNTs and tuning the thermodynamic and kinetics conditions, the selective distribution of MWCNTs in interfacial PS phase were formed after melt mixing. These composites displayed ultralow conductive percolation threshold and excellent electromagnetic shielding effectiveness by this structuring process. (C) 2015 Elsevier Ltd. All rights reserved.