The organic–inorganic hybrid nanocomposite of polyaniline–V2O5 was synthesized by microwave-assisted hydrothermal method. The nanocomposite was separated by filtration and washed with deionized water. Structural study of nanocomposite was performed using XRD. The microstructural study of nanocomposite performed using field emission scanning electron microscopy (FESEM) shows self-assembled plates with curly petal or tremella-like morphology. The nanocomposite was subjected for spectroscopic (UV–vis and FT-IR) analysis. The UV–vis spectra revealed the presence of conducting emeraldine salt phase of the polymer which was further supported by FT-IR analysis.