It is of both practical and scientific significance to understand the temperature dependence of contact angles of water on various surfaces. However, the variation trend of water wettability on a smooth hydrophobic surface with increasing temperature remains unclear. In this work, in situ characterization of the contact angle of water on Teflon (polytetrafluoroethylene) surfaces and the interfacial tension of water over a temperature spectrum from ∼25 to 160 °C under pressurized conditions (2, 3, and 5 MPa) in a nitrogen atmosphere was conducted by employing the sessile drop and pendant drop methods, respectively. A nearly invariant trend of the contact angle was observed over the entire temperature and pressure range. As expected, however, it was shown that the water-N2 interfacial tension almost linearly declines with increasing temperature and that pressure has a negative effect on the interfacial tension. Based on the theory of surface thermodynamics, the effects of temperature on the contact angles were analyzed in combination with the gas adsorption effect. Estimations on the solid-gas interfacial tension, surface entropy, and the heat of immersion were made to gain more insights into the temperature dependence of the water contact angle on a smooth hydrophobic surface.