We successfully decorated multi-wall carbon nanotubes (MWNTs) with silver by reacting Ag-NPs with thiolfunctionalized MWNT-SH. Ag alkylcarbamate complex was used as an Ag precursor. Uniform Ag-NPs (5-10 nm) were effectively prepared by microwaving within 60 s using 1-amino-4-methylpiperazine (AMP), which acts as a reaction medium, reducing agent, and stabilizer. The MWNTs were functionalized with 2-aminoethanethiol. Exploiting the chemical affinity between thiol and Ag-NPs, Ag-MWNT nanohybrids were obtained by spontaneous chemical adsorption of MWNT-SH to Ag through Ag-S bonds. The Ag-S-MWNTs were characterized by TGA, XRD, and TEM to confirm that Ag-NPs were uniformly decorated onto the MWNTs. The Ag-S-MWNTs were then employed as conducting filler in epoxy resin to fabricate electrically conducting polymer composites. The electrical properties of the composites were measured and compared with that containing MWNT-SH. The electrical conductivity of composites containing 0.4 wt % Ag-S-MWNT was four orders of magnitude higher than those containing same content of MWNT-SH, confirming Ag-S-MWNT as an effective conducting filler.