In the nanoscale architecture, expected morphology plays an important role in the fabrication of supercapacitive devices due to their highly porous properties. Herein, a well-defined rutile TiO₂ architecture was successfully prepared by spray pyrolysis technique (SPT), by changing the concentration of the spraying solution from 0.01 to 0.1 M at 723 K deposition temperature onto stainless steel substrates. The thermal decomposition behavior of the precursor is analyzed using thermogravimetric analyzer. As-deposited thin film electrodes exhibits rutile tetragonal crystalline structure confirmed using XRD. FT-IR study indicate the presence of Ti=O stretching vibration in the range 400–1000 cm⁻¹. The obtained nanostructures merely changes by changing the concentration of spraying solution and process parameters as strongly evidenced using SEM. TEM image and SAED pattern confirms the formation of nanorods and rutile tetragonal structure of TiO₂. EDAX confirms formation of pristine TiO₂. Wettability of samples shows angle of contact changes by changing the sample thickness and surface roughness of the samples. Optimized electrode shows maximum specific capacitance 273.84 F/g at 2 mV/s in 1 M KOH. Maximum values of specific energy (SE), specific power (SP) and efficiency as observed using galvanostatic charge–discharge are 04.32 Wh/Kg, 70.27 KW/Kg and 90.37%, respectively.