We examine the contact angle of water droplets on polystyrene (PS) thin films of varying thicknesses supported by silicon wafers under both air and pressurized carbon dioxide (CO2) environments. At 23 degrees C, the contact angle is found to increase upon increasing CO2 pressure in the vapor regime and then levels off in the liquid CO2 regime. A macroscopic model based on Young's equation and the geometric-mean method for interfacial tensions, and long-range van der Waals interactions, correctly predicts the trends and the magnitude of the contact angle dependence on pressure, although deviations occur at high CO2 activities. The contact angle was also found to depend on film thickness, h, when h was comparable to or smaller than 50 nm. Specifically, the contact angle decreases with decreasing PS film thickness. This behavior could be accounted for with the use of a model that incorporates the effects of film thickness, CO2 pressure, and the long-range van der Waals potential.