The current work describes room-temperature gas sensing performances using an oligoacenaphthylene (OAN)/p-hydroxyphenylacetic acid (p-HPA) composite. Based on inverse gas chromatography (IGC), the London dispersive surface energy γ_s^d is calculated by using 14 representative models. Even when the γ_s^d values of both OAN and the OAN/p-HPA composite are decreased as the temperature increases, the surface of OAN shows a higher value than that of the composite. The Gibbs surface free energy values of both are decreased with an increasing temperature. In our results, higher Lewis basic characters are observed in OAN and the OAN/p-HPA composite and the OAN/p-HPA surface exhibits a higher basicity compared to OAN. Because of the presence of phenolic groups in the OAN/p-HPA composite, the more important basic character drives a significant CO gas sensing ability with a sensitivity of 8.96% and good cycling stability as compared to the pristine counterparts. It is expected that the current study sheds light on a new pathway to exploring polymer composite materials for futuristic diverse and multiple applications, including IGC and gas sensor applications.