Vanadium oxides V 2 O 5 and V 2 O 3 have been synthesized by ultrasonic spray pyrolysis in the form of nanostructured spherical agglomerates with an average diameter of 0.5-1.5 µm. By changing the synthesis conditions, the vanadium oxidation state and microspheres surface morphology can be varied. The microspheres of V 2 O 5 are formed during aerobic synthesis, while V 2 O 3 microspheres are produced under an atmosphere of argon. An increase in the concentration of the initial solution leads to an increase in both size of V 2 O 5 nanoparticles and the diameters of the V 2 O 5 microspheres. Long-term storage of V 2 O 3 in air results in morphological degradation of the microspheres.