The synthesis of cobalt acetylenedicarboxylate (fCo2) and polymerized cobalt acetylenedicarboxylate(hCo2) using acetylenedicarboxylic acid (fADC) has been reported. Surface morphologies were analyzedusing scanning electron microscope (SEM) and transmission electron microscope (TEM). The UV–visabsorption and infrared spectroscopies were used for optical characterization. Structural properties werestudied using X-ray diffractometer with scattering vector analysis. The minimum particle size was foundto be 10 nm for polymerized acetylenedicarboxylate and confirmed through the TEM analysis. Ther-mal properties were investigated using thermal gravimetric analysis (TGA) and differential scanningcalorimeter (DSC). Further, the LPG sensing properties of the materials were investigated at room tem-perature (25◦C). Polymerized acetylenedicarboxylate shows larger variation in resistance in comparisonto acetylenedicarboxylate and acetylenedicarboxylic acid both. In addition, the possible sensing mecha-nism of the interactions of LPG on the surface of the materials has been discussed. The maximum sensorresponse, small response time and long-term stability demonstrates that the fabricated sensor (hCo2) ischallenging for the detection of LPG.