Hierarchically ZnO nanoarchitecture synthesized through coprecipitation technique. Growth process has been analyzed by varying pH from 5.5 to 13 along with post heat treatment process through the observation of surface morphology from 2D plates, triangular, hexagonal rods, needles, and finally to hierarchical. X-ray diffraction (XRD) reveals many intermediate phases along with ZnO which has been eliminated through the proper pH and temperature. The native defects have been discussed by using Raman and positron annihilation spectroscopy. Further, multifunctional properties of synthesized material have been discussed by candle-like warm white luminescence, photocatalysis, electrocatalysis and energy storage applications. Specially hierarchically nanoarchitecture found suitable for warm white lighting along with effective for waste water treatment by visible light. The highly porous property of the same material made itself appropriate for effective oxygen evaluation reaction and hydrogen evolution reaction together with reduced overpotential and Tafel slope. The application for supercapacitor electrode (~780 F/g) also has been revealed which opened new dimension for hierarchical ZnO.