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The surface characteristics of wood veneer are inevitably influenced by hot compression treatment, which is crucial to bonding ability in the production of veneer-based composites such as plywood and laminated veneer lumber (LVL). The objective of this study was to investigate the effect of compression at the temperature of 120 °C on the surface roughness, surface element compositions, and surface free energy (SFE) of poplar veneer. The results showed that the surface roughness of veneer decreased with increasing compression ratio (CR). X-ray photoelectron spectroscopy (XPS) analysis indicated that the oxygen to carbon atoms ratio (O/C ratio) of the veneer surface decreased, while the carbon C1 to C2 atoms ratio (C1/C2 ratio) increased due to hot compression. The SFE of veneer increased by 12% at the CR level of 11%. The improvement in wettability was mainly due to the interfacial contact area increase of the hydrophilic veneer and the decrease in hydrophobic air in the liquid-veneer interface as the CR level increased.