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In recent years, conductive polymer composites have found applications as gas sensors because of their sudden change in electric resistance of several orders of magnitude when the materials are exposed to certain solvent vapors. However, the composites having this function reported so far are mostly based on crystalline polymeric matrices, which factually sets a limit to materials selection. The present work prepares polystyrene/carbon black composites through polymerization filling and proves that the amorphous polymer composites can also serve as gas sensing materials. The composites' percolation threshold is much lower than that of the composites produced by dispersive mixing. In addition, high responsivity to some organic vapors coupled with sufficient reproducibility is acquired. The experimental data show that molecular weight and molecular weight distribution of the matrix polymer and conducting filler content exert great influence on the electrical response behavior of the composites. As a result, composites performance can be purposely tailored accordingly. Compared with the approaches of melt‐blending and solution‐blending, the current technique is characterized by many advantages, such as simplicity, low cost, and easy to be controlled. Effect of different organic solvent vapors on the electric resistance of PS/CB composites (CB content = 10.35 vol.‐%).magnified imageEffect of different organic solvent vapors on the electric resistance of PS/CB composites (CB content = 10.35 vol.‐%).

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