The surface physicochemical properties of hydroxyl terminated polybutadiene (HTPB) were studied by means of inverse gas chromatography（IGC）. The dispersive component of the surface free energy of HTPB, as well as the total surface free energy decreases as the temperature increases. Compared with the polyethylene， HTPB has higher surface free energy because there are some hydroxyl groups on the surface of the HTPB molecule. While the proton donor and the proton acceptor components increase with the increase of the temperature, the proton donor one is more sensitive to the temperature and increases more rapidly. The results show that HTPB has higher dispersive component and shows stronger Brnsted acidity.