The chemically modified multiwalled carbon nanotubes (MWCNT)/poly(1-vinyl-1,2,4-triazole) (PVTri) composites were prepared via in situ emulsion polymerization. The morphological and structural properties of the surface-modified MWCNT and the synthesized MWCNT/PVTri composites were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The electrical properties of the composite material were analyzed by conductivity measurements. The thermal analysis and the T-g value of the polymer were determined by differential scanning calorimetry technique. The obtained novel MWCNT/PVTri composites exhibited excellent solubility and possessed a slightly higher glass transition temperature than that of the pure polymer.