Polyaniline/graphene (PANI/GN) nanocomposites were fabricated via in‐situ oxidative polymerization of aniline in the presence of cetyltrimethylammonium bromide (CTAB) modified graphene (CGN) in 1M hydrochloric acid (HCl) solution. The morphology and structure of PANI/GN samples were investigated by Fourier transform infrared spectrum, X‐ray diffraction, ultraviolet and visible spectrum, thermogravimetric analysis, field‐emission scanning microscope (FE‐SEM), and transmitting electron microscopy (TEM). The conductivities of the PANI/GN nanocomposites were measured using four‐probe electrical conductivity measurement. The results indicated that the GN sheets disperse into the form of monolayer or stack few layers in PANI matrix. The GN sheets serve as a support material for PANI particles and the structure of GN covered with PANI nanoparticles were confirmed by FE‐SEM and TEM. The electrical conductivities of the PANI/GN samples have been improved compared with pure PANI prepared in the similar condition. POLYM. COMPOS., 36:1767–1774, 2015. © 2014 Society of Plastics Engineers