An economically viable solution-based approach was employed for fabrication of nanostructured BiVO4. The evolution of physiochemical and electrochemical features with respect to the synthesis temperature was analyzed using structural, morphological, and electrochemical analysis. When utilized as a supercapacitor electrode, in 3-electrode setup, the BiVO4 exhibited highly impressive specific capacity of 1864 Cg−1 at a high current density with battery type behavior. Also, this attractive material exhibits very lesser charge transfer resistance of 4 Ω, which is highly beneficial for performing charge/discharge at higher current rates. Further, this material retained 84% of its initial capacity after 3000 repeated charge discharge cycles. The behavior of the same electrode material can be either battery-like or pseudocapacitive, depending on its shape, size, and intercalation ion. Although it can be challenging to draw a precise border, the range of b values between 0.5 and 1.0 denotes a “transition” area between pseudocapacitive and battery-type materials. It is important to note that when the reaction temperature rises from 140 °C to 160 °C, 180 °C, and 200 °C, more electroactive sites emerge, leading to improved electrochemical performance. The battery type behavior is dominated as the reaction temperature is increased from 140 °C, and it is consistent with the voltagram analysis.