Present work portrays the surface morphology dependent electrochemical behaviors tuned by annealing the chemical bath deposited (CBD) cerium oxide electrodes. The altered nanostructure properties are well-supported by in-depth structural and morphological analysis. Cerium oxide electrode annealed at 200 degrees C exhibits good surface properties enabling maximum electro-active porous cavities to penetrate electrolyte ions towards enhanced electron transfer. Consequently, the electrode exhibits maximum specific capacitance of 750 F/g with remarkably stable charge-discharge cycles. Fabricated symmetric solid-state supercapacitor device impressively expands potential window to 1.2 V with the aid of PVA-LiClO4 gel electrolyte with a peak specific capacitance of 321.3 F/g with top-up of 61.4 Wh/kg specific energy. The series combination of two devices confirms the strong energy storage ability by glowing 'VNIT' acronym designed through 21 red LEDs from the practical point of view.