The ability to control the shape, structure and faceting characteristics of bimetallic alloy nanocrystals (NCs) has been vital for designing a catalyst with excellent activity and durability in fuel cells. However, it has remained a significant challenge to synthesize platinum–copper (Pt–Cu) alloy NCs with controlled structure and exposed facets. Herein, Pt–Cu alloy NCs with different shapes, structures and facets were synthesized via a one-step direct chemical co-reduction method employing various glucose concentrations. The results showed that the prepared Pt–Cu alloy NCs exhibited very interesting facet-dependent electrocatalytic properties for ethylene glycol oxidation. In comparison with other prepared Pt–Cu alloy NCs and commercial Pt/C, Pt–Cu alloy NPs with (111)-dominant facets showed higher electrocatalytic activity and durability for ethylene glycol oxidation. Alloy NPs showing prominent electrocatalytic performance were attributed to the predominant (111) facets on NP surfaces serving as catalytic active sites, in addition to added Cu providing unique electronic and synergistic effects. The present work highlighted that these NPs with (111)-dominant facets were indeed promising candidates as electrocatalysts with excellent activity and superior durability.