In the present work, organic/inorganic hybrid nanostructures comprised of polyaniline and vanadium oxide were synthesized via a simple hydrothermal technique. The polyaniline/vanadium oxide hybrid morphology was tailored from rods to spheres by controlling the relative concentration of the reactants. The synthesized composites were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FESEM) for structural and morphological analyses. Electrorheological (ER) properties of the as-prepared nanocomposites suspended in silicone oil were investigated by a rotational viscometer under both steady and dynamic shear. The ER activity of the composite material suspensions showed higher ER effects for the product with the rod-like structures than for the product with the sphere-like structures. The typical ER behaviour showed by the polyaniline-vanadium oxide nanocomposites demonstrated their potential application as an ER smart material.