The wetting phenomena and surface energetic behavior in heat-treated bamboo were studied. The bamboo specimens were heat-treated at temperatures of 100, 140, and 180 °C for 4 h, and an untreated sample served as a control. The sessile drop technique was used to estimate the surface contact angles of the control and heat-treated bamboo samples. The contact angle data were then used to determine the surface free energies using the Lifshitz-van der Waals/acid-based approach. The results revealed that the heat treatment process affects surface wettability. Heat treatment at 100 to 180 °C increased the contact angle of distilled water and formamide, but heat treatment did not cause any increase in the contact angle of diiodomethane. The hydrophobic characteristics of the bamboo surfaces also increased under heat treatment, and the surface free energy and the polarity of the bamboo decreased. Surface analysis by XPS of the samples heat-treated at 180 °C showed a decreased O/C ratio and increased C1 peak, indicating that more lignin and extractives were situated on the bamboo surface. Changes in wettability can greatly impact the use of the material, particularly with respect to the adhesion of paints and coatings.