By using the low loading of the conductor filler to achieve high conductivity is a challenge associated with electrically conductive adhesion. In this study, we show an assembling of nickel-coated polystyrene (Ni@PS) microspheres into 3-dimensional network within the epoxy resin with the assistance of an electric field. The morphology evolution of the microspheres was observed with optical microscopy and scanning electron microscopy (SEM). The response speed of Ni@PS microsphere to the electric field were investigated by measuring the viscosity and shear stress variation of the suspension at a low shear rate with an electrorheological instrument. The SEM results revealed that the Ni@PS microspheres aligned into a pearl-alike structure. The AC impedance spectroscopy confirmed that the conductivity of this pearl-alike alignment was significantly enhanced when compared to the pristine one. The maximum enhancement in conductivity is achieved at 15 wt. % of Ni@PS microspheres with the aligned composites about 3 orders of magnitude as much as unaligned one, typically from ~10−5 S/m to ~10−2 S/m.
