The most stable oxide of the vanadium oxide family is V2O5. A lot of research effort is focused on it because it has a multitude of functional applications. Here we report on how the heat treatment (600°C, 5 h, air) affects the microstructure and hence, the band gap of V2O5. The V2O5 powders, initially obtained by simple thermal dissociation (500 °C, 3 h, air) of ammonium metavanadate, followed by heat treatment of pellets; were studied. The structural and optical studies performed using X-ray diffraction (XRD), FESEM and UV-Vis techniques, provide uniquely interesting results which indicate the possibility of band gap tuning by controlling the microstructure.