In this paper, we report a facile and green method to synthesize Au nanorods (AuNRs)/graphene oxide (GO) nanocomposites. In this approach, cetyltrimethylammonium bromide (CTAB) acted not only as a shape-directing agent but also as an assembling agent. The AuNRs/GO nanocomposites were prepared through electrostatic self-assembly between CTAB-capped positively charged AuNRs and negatively charged GO in an aqueous solution without introducing other assembling agents or surfactants. The catalytic performance of the obtained catalysts is evaluated with TOF, TOF1/2 and k(app) values. Due to the increased effectiveness from the charge-mediated assembly, these AuNRs/GO nanocomposites showed high performance in the catalytic reduction of 4-nitrophenol to 4-aminophenol. The AuNRs/GO ratio was optimized, and the nanocomposite with a mass ratio 1:0.4 showed the best catalytic activity, achieving a k(app) value of 1.69 min(-1), which was not only 19.7 times better than the AuNRs, but also significantly better than the catalytic performance of Au/graphene and Au/GO composites reported in the literature.