This paper is a report on synthesis and analysis of the structure, morphology, and physicochemical properties of a three-component-Polyaniline/Chitosan/Co3O4 - (CPAESCO)-hierarchical core/shell ternary nanocomposite. This was achieved by Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermo Gravimetric Analysis (TGA), Electrical Conductivity and UV-Visible analysis. The chemical bonding established in the composites were confirmed by using FT-IR. XRD patterns helped analysis of intensity variation of Co3O4 peaks, polyaniline (PAES) peaks, Crystallite size (D) and inter-crystallite separation (R) of the composites. Thermal stability increases and electrical property shows a step wise increase with increase in nanoparticle addition. Morphological changes from granular PAES to plate like CPAESCO is visible in SEM. The polaron lattice structures, hypsochromic shift, and crystallite size dependent band gaps in CPAESCO due to energy confinement produced from ligand-metal charge transfer (LMCT) interaction of Co3O4 in PAES matrix, are visible in UV-Vis spectra. The improved properties of the composite are as a result of the formation of core/double shell as shown in TEM. This nanocomposite can be used in optoelectronic and biomedical applications, catalysis, chemical and bio sensors, and energy storage devices because of its enhanced properties. (C) 2015 Elsevier B.V. All rights reserved.