Abstract: Poly(phenylene sulfide) (PPS) is an insulating and hydrophobic material, which somewhat limits its certain applications in some specific fields. The amino-group modified PPS (NPPS) was prepared, and NPPS was further modified with epoxy-functionalized muti-walled carbon nanotubes (EFMWCNTs) by solution blending method via covalent interaction, and EFMWCNTs/NPPS conductive composites were prepared. The structure and properties of composites were characterized by various techniques including FTIR, XPS, XRD, FESEM, TEM, DSC, TGA and semiconductor powder resistivity tester. Characterization results show that when amino-group was introduced into the chain segment of PPS, the melting peak and crystalline peak of PPS disappear. After NPPS is further modified with EFMWCNTs, compared with NPPS, the thermal stability of EFMWCNTs/NPPS conductive composites increases because EFMWCNTs were attached onto NPPS by covalent bond which is effective to disperse EFMWCNTs into NPPS matrix. Electrical conductivity of EFMWCNTs/NPPS composites increases with the increase of EFMWCNTs content. The electrical conductivity of composite is 6.1×10^-2 S/cm with loading 10wt% EFMWCNTs.