A hybrid nanocomposite of polypyrrole (Ppy)–V2O5 has been fabricated and characterized for better understanding of material enabling one to use this for appropriate application as the nanocomposite shows better thermal stability. The characterization has been done using XRD, FT-IR, FESEM, and UV–Vis for their structure, surface morphology, respectively, along with TGA and two-probe method used for checking thermal stability, and DC electrical conductance and dielectric behavior of the electrical phenomena of sample. The analysis of XRD demonstrates that crystallinity of nanocomposites is the same as that of the polymer, even though interaction between conducting Ppy and V2O5 is present as evident from FT-IR spectroscopy. A variation in bandgap, in comparison with Ppy, is observed when V2O5 is added into it. The microstructural study of nanocomposites shows encapsulation of V2O5 particles in Ppy matrix with changes in morphology with increase in doping. Conductance results show that electrical conductivity of Ppy decayed on adding V2O5. It has also been found that addition of V2O5 in Ppy has noticeable effect on the dielectric properties.