Since a few years ago, a topic of curiosity consists in evolving composites filled with the nanofillers to improve various properties of polymer matrix. This work aims to investigate the structure–property relationship in ternary nanocomposites containing of amorphous poly(vinylpyrrolidone) as the matrix, organo-modified-TiO₂ nanoparticles and organo-modified-montmorillonite as the nanofillers. In this regard, poly(vinylpyrrolidone)/organo-modified-TiO₂/organo-modified-montmorillonite nanocomposites were prepared by sonication process with 10 wt% of organo-modified-TiO₂ and different loadings (3, 5 and 7 wt%) of organo-modified-montmorillonite. Nanostructure characterization and dispersion capacity of nanofillers in the polymer matrix were investigated by X-ray diffraction, transmission electron microscopy and field emission scanning electron microscopy. According to these data, the nanostructure of ternary nanocomposites was predominantly intercalated. Also, incorporation of the organoclay and TiO₂ nanoparticles into the poly(vinylpyrrolidone) system was observed to have an obvious effect on the shape and size of polymer matrix. According to thermogravimetric analysis data, the presence of organo-modified-montmorillonite and organo-modified-TiO₂ in the poly(vinylpyrrolidone) matrix, caused an improved in the thermal stability of the obtained poly(vinylpyrrolidone) nanocomposites.