A composite of Multiwalled Carbon Nanotubes (MWCNTs) and polyaniline (PAni) was synthesized by in situ oxidative polymerization of aniline monomers on poly (sodium 4-styrenesulfonate) (PSS) dispersed MWCNTs to produce coaxial structures of MWCNT-PAni composite. The structural, morphological, thermal, surface, and capacitive properties of the composite were analyzed. Scanning electron microscopy images of the composite revealed nanofibrous structure. Infrared spectrum showed slight shifts for several bands of the composite from the bands of PAni to suggest that the MWCNTs have strong attractive interactions with the PAni backbone. The composite was fabricated onto a graphite electrode and the fabricated electrode was characterized using cyclic voltammetry. The fabricated electrode exhibited specific capacitance fig 1, and the value retained 82.5% after 800 cycles. Owing to the good capacitance behavior and cycling stability, the synthesized composite holds promise for energy storage devices like supercapacitors.