The many uses of wood are greatly affected by its surface properties, which are significantly altered by heat treatment. Investigated here are the wettability and surface brittleness when treating poplar wood with heat at 160, 180, 200, and 220 °C for 2 h. Contact angles were measured by the sessile drop method, and surface free energy was calculated. Surface brittleness was expressed by hardness (HD value), roughness (Ra, Rq, Ry, and Rz values), and abrasive resistance (K value). Next, non-destructive Fourier transform near-infrared spectroscopic (FT-NIR) and X-ray photoelectron spectroscopic (XPS) measurements were employed to analyze the surface chemical changes. Scanning electron microscopy (SEM) revealed the post-heating microscopic structure. The results demonstrated that heat treatment reduces the surface wettability while increasing the surface brittleness, which becomes more apparent with increased temperature. Significant differences were determined (p < 0.05) between the surface parameters at four different temperatures. The degradation of cell wall components and the deterioration of microstructures was further expounded by FT-NIR, XPS, and SEM analyses. Furthermore, the abrasive resistance and hardness values decreased in line with the rate of weight loss (WL, %) and temperature. This indicates a strong correlation between the surface characteristics and the WL or temperature. The intensity of heat treatment appears to be predictable and easy to regulate.