Thermophysical molding (TPM) treatments can significantly improve the surface properties of thick wood veneer. To understand the effects of TPM treatments on the surface properties of thick veneer, the roughness, contact angles, and chemical changes were determined. The results indicated that the roughness of the thick veneer decreased when the temperature and the duration increased. The contact angles decreased when the temperature increased, resulting in better wettability. X-ray photoelectron spectroscopic (XPS) results provided information about the significant chemical changes in the surface with different TPM temperatures of 160–190 °C and durations of 5–11 min. Increases in temperature and duration increased the C content and decreased the O content during the treatment process. The most significant changes in the thick veneer that resulted from increasing the temperature and the duration were the increase in the C1 component and the decrease in the C2 component. Thus, the oxygen to carbon (O/C) ratio decreased and the ratio of aromatic carbon to aliphatic carbon (C1/C2) notably increased with the increasing TPM temperature. The TPM duration slightly affected the O/C ratio, but it had a stronger linear relation with the C1/C2 ratio. Additionally, the C1/C2 ratio and the O/C ratio had a linear statistical relationship with the initial wettability. These findings could provide useful information for the future utilization of thick veneers treated with TPM.