The present work focuses on the design and development of highly oriented well aligned nano shrubs of polyaniline decorated Co3O4 (COP) and demonstration as an efficient electrode for the fabrication of supercapacitors. Morphological results suggest that COPs are composed of PANI nano shrubs grown from the pores of Co3O4 to form a three-dimensional nanostructure. Further, supercapacitor with the configurations of [(indium tin oxide)ITO-COP/1 M Na2SO4/COP-ITO] was fabricated and its performance evaluated leading to high specific capacitance value (1151 F g−1 @ 3 A g−1), high rate performance of 70% at the current density ranging from 3 to 20 A g−1, and excellent cycling stability (92% after 5000 cycles @ 10 A g−1). The excellent performance of this hybrid nanocomposite is attributed to well aligned self-assembled structural advantage of COP and the synergistic effects of cobalt oxide and polyaniline which is responsible for the substantial reduction in the charge transfer resistance as revealed by electrochemical impedance spectroscopy. All these results suggest that the developed strategy can be used for the development of efficient hybrid conductive nanocomposite based electrode material for other combinations of transition metal oxide-conductive polymer based supercapacitors.