Pd-based electrocatalysts for direct liquid fuel cells (DLFCs) have drawn significant attentions as an energy system ideal for automobile, unmanned aerial vehicles and portable electronic devices owing to their high power density. Typical strategies, including optimization of shape or facet, and composition control, have been investigated to enhance the activity and of Pd-based catalysts and study their enhanced catalysis mechanism. However, those were significant and challenging for development of advanced catalysts toward direct liquid fuel cells (DLFCs). This presentation reports the synthesis and characterization of (100)-faceted β-PdH cubes and (111)-faceted β-PdH octahedra for the first times. Those facet controlled β-PdH nanocrystals and Pd conterparts can offer an opportunity to investigate the link between the catalytic kinetics and shape/facet/composition of the catalysts. The β-PdH cubes and octahedra remarkably accelerate the catalytic activity and stability toward formic acid/methanol oxidation reaction (FAOR/MOR) due to ligand effect originated from the interstitial alloying of β-PdH. The formation and ligand effect of facet controlled β-PdH nanocrystals were confirmed by a number of techniques, including scanning transmission electron microscopy, X-ray analysis, H₂-temperature programmed reduction, and electrochemical measurements. FAOR/MOR activities of β-PdH nanocrystals and Pd conterparts are also presented.