In this paper, the efficiency of plasmon-driven catalytic reaction on double nanowires was investigated experimentally. The dimerization of 4-nitrobenzenethiol (4NBT) to p,p’-dimercaptoazobenzene (DMAB) can be driven by hot electrons generated by the non-radiative decay of surface plasmons, which can be monitored by Raman spectroscopy. It was demonstrated under the same excitation conditions, the Raman signal of the reactant molecules on the double nanowires was significantly stronger than that on the single nanowire. So does the catalytic reaction efficiency. The electromagnetic field intensity distribution of a single nanowire and double nanowires under the same excitation condition was analyzed through the finite difference time domain (FDTD) simulation . It was shown that the stronger “hot spot ” in the double nanowire part is induced. The theoretical and experimental results were consistent with each other. This research may provide a new way for catalytic reactions driven by double nanowire plasmonic structure.