In this study, single-crystal Pd nanocrystals with exposed (100) and (111) facets were prepared and their catalytic performance were compared in 2-ethylanthraquinone hydrogenation reaction through immobilization on γ-Al₂O₃ as catalyst. Our experimental results combined with density functional theory calculations showed that the Pd (100) facet was more active than Pd (111) in CO hydrogenation but less active in saturation of aromatic rings. Directed by this result, a high-performance Pd/γ-Al₂O₃ nanocatalyst was successfully prepared using a one-step synthesis method, which could not only control the exposure of the Pd (100) facet but also increase the stability of Pd components. This catalyst exhibited superior catalytic performance with a hydrogenation efficiency of up to 15.0 g L⁻¹ and a selectivity of 99.1% under mild reaction conditions (0.2 MPa, 50 °C, 15 min), which was superior to that of the catalyst prepared by an impregnation method.