Morphology controlled high aspect ratio worm-like polyaniline (PANI) layer coated Au-nanostructures (Au/PANI) have been successively synthesized by in situ polymerisation techniques using aniline as a monomer with HAuCl4 as an oxidising agent in the absence and presence of citric acid (CA). Synthesized composites were characterized by HRTEM, FESEM, XRD, XPS, UV-vis and FTIR study. Spherical morphologies are seen in the absence of CA and Au nanoparticles are coated by a PANI thin layer with ∼30 nm thickness. In the presence of CA, as well as depending upon the CA to aniline molar ratio, morphology varies from irregular assembly to regular fiber to spherical-like nanostructures. The nanostructures show fibrous morphology with an average diameter of ∼100 nm and lengths of more than 5 μm when CA to aniline molar ratios are 1.0 and 0.2. When the ratios are 2.0 and 0.1, the nanostructure represents the granular-like morphology. Nanofiber formation takes place by the assembly of the CA capped tiny Au-nanorods in the presence of aniline during the polymerisation, and all Au-nanorods are finely coated by a PANI thin layer of ∼5 nm thickness. Importantly, fibrous Au/PANI nanostructures show superior catalytic activity compared to spherical/irregular Au/PANI nanostructures towards the reduction of toxic aromatic nitro compounds like 4-nitrophenol (4-NP), 4-nitroaniline (4-NA), 2,4-dinitrophenol (2,4-DNP) and 2,4,6-trinitrophenol (2,4,6-TNP). This is because of the coating thickness of PANI over Au-nanoparticles in fibrous Au/PANI nanostructures as well as enhanced surface area.