Direct ethanol fuel cells (DEFCs) are a promising power source, but the low selectivity to ethanol complete oxidation is still challenging. The localized surface plasmon resonance (LSPR) excitation has been reported to accelerate and drive several chemical reactions, including the ethanol oxidation reaction (EOR), coming as a strategy to improve catalysts performance. Nonetheless, metallic nanoparticles (NPs) that present the LSPR excitation in the visible range are known for leading to the incomplete oxidation of ethanol. Thus, we report here the application of gold-rhodium nanoflowers (Au@Rh NFs) towards the plasmon-enhanced EOR. These hybrid materials consist of a Au spherical nucleus covered by Rh branches shell, combining plasmonic and catalytic properties. Firstly, the Au@Rh NFs metallic ratio was investigated in dark conditions to obtain an optimal catalyst. Experiments were also performed under light irradiation. Our data demonstrated an improvement of 352% in current density and 36% in selectivity to complete ethanol oxidation under 533 nm laser incidence. Moreover, the current density showed a linear increase with the laser power density, indicating a photochemical effect and thus enhancement due to the LSPR properties.