Carbon-supported PtRh nanoparticles with preferential (100) orientation was prepared by an alcohol-reduction process using KBr as a shape directing agent. The electrocatalysts were characterized by EDX (energy-dispersive X-ray analysis), XRD (X-ray diffraction) and TEM (Transmission electron microscopy). The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature in acid medium. On-line differential mass spectrometry experiments were performed on a single cell of a direct ethanol fuel cell (DEFC) at 60 0C and the anodic effluents were analyzed by ATR-FTIR. PtRh/C (100) electrocatalyst showed cubic-like morphology and average nanoparticles size of 8 nm and provided superior DEFC performance (density power per Pt active area) and CO2 selectivity compared to polycrystalline PtRh/C and commercial Pt/C electrocatalysts.Conselho Nacional de Desenvolvimento Cient??fico e Tecnol??gico (CNPq)Funda????o de Amparo ?? Pesquisa do Estado de S??o Paulo (FAPESP)CNPq: 305622/2020-0FAPESP: 17/11937-4; 18/04596-9; 18/04595-2