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The thermally expandable microspheres (TEMs) were prepared through suspension polymerization with acrylonitrile (AN), methyl methacrylate (MMA) and methyl acrylate (MA) as the main monomers. Simultaneously, iso-pentane, n-hexane, iso-octane and other low-boiling hydrocarbons were prepared as blowing agents under two conditions, including high-pressure nitrogen and atmospheric conditions. The above physical foaming microspheres have a core-shell structure and excellent foaming effects. A layer of polyaniline (PANI) was deposited on the surface of the prepared TEMs by emulsion polymerization to obtain conductive and heat-expandable microspheres. Afterwards, the foaming ink was prepared by mixing the conductive TEMs and water-based ink. Finally, a conductive three-dimensional picture was obtained by screen-printing technology. This paper specifically focuses on the effects of particle size, morphology and the thermal expansion properties of the microspheres. The present research methods expect to obtain microspheres with a high foaming ratio, uniform particle size and antistatic properties, which may be applied to physical foaming ink.