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To reveal the role of crystalline polymers in carbon black (CB) filled amorphous polymer composites and improve the mechanical properties of composite films, CB/poly(ethylene glycol) (PEG)/poly(methyl methacrylate) (PMMA) composites were synthesized by polymerization filling in this work. The electrical conductive property and response to organic solvent vapors of the composites were investigated. The composites, characterized by a relatively low percolation threshold ( 2.1 wt %), had lower resistivity than CB/PMMA composites prepared with the same method because of the different dispersion status of CB particles in the matrix polymer. The concentration and mo-lecular weight of PEG notably influenced the electrical response of the composites against organic vapors. The drastic increase in the electrical resistance of the composites in various organic vapors could be attributed mainly to the swelling of the amorphous polymer matrix in the solvent but not to that of the crystalline polymer. These findings could help us to understand the conductive mechanism and electrical response mechanism of the composites as promising gas-sensing materials.