The novel high-performance nanocomposites of polyaniline (PANI) and graphene oxide sheets (GOs) was synthesized via in situ polymerization in the presence of Hexadecyl trimethyl ammonium Bromide intercalated graphite oxide (CGO), basing on PANI and GOs as a matrix respectively. The result showed that ANI monomer was intercalated into the spacing of CGO, and the CGO was well exfoliated into nanosheets while polymerization. Owing to π–π electron stacking effect between the PANI and the GOs, the electrical conductivity of GOs/PANI nanocomposites (0.47 S/cm), which basing on PANI as a matrix, improved in comparison with pure PANI nanowires (0.02 S/cm) and GO (2.5×10-5 S/cm), while the electrical conductivity of PANI/GOs nanocomposites, which basing on GOs as a matrix, was only 6.2×10-3 S/cm. And it also indicated that the mole ratio of APS, the concentration of HCl, other with the polymerization time, are also important influencing factors of the conductivity of nanocomposites. The novel high-performance nanocomposites of polyaniline (PANI) and graphene oxide sheets (GOs) were synthesized via in situ polymerization in the presence of Hexadecyl trimethyl ammonium Bromide intercalated graphite oxide (CGO), basing on PANI and GOs as a matrix respectively. Owing to π-π electron stacking effect between the PANI and the GOs, the electrical conductivity of GOs / PANI nanocomposites (0.47 S / cm), which basing on PANI as a matrix, improved in comparison with pure PANI nanowires (0.02 S / cm) and GO (2.5 × 10-5 S / cm), while the electrical conductivity of PANI / GOs nanocomposites, which basing on GOs as a matrix, was only 6.2 × 10 -3 S / cm. And it also indicated that the mole ratio of APS, the concentration of HCl, other with the polymerization time, are also important influencing factors of the conductivity of nanocomposites.