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In this article, multiwalled carbon nanotubes (MWNT) soluble in common organic solvents are prepared. The solubility is conferred to the MWNTs by covalent attaching of appropriately modified poly(vinyl chloride)(PVC). The nucleophilic substitution of PVC with potassium 4-hydroxythiophenolate is carefully studied. It proceeds through a stereoselective mechanism. The subsequent esterification reaction of the hydroxyl pendant groups in the modified PVC (mPVC) with carboxylic acids created in MWNT is reported. The intermediates and final products are characterized by FTIR, 1H and 13C NMR, and Raman spectroscopy. The thermal stability as well as the molecular dynamics of the MWNT-modified PVC (MWNT-mPVC) are studied. The potential applications of the PVC-functionalized carbon nanotubes and the demonstrated functionalization strategy are discussed.