A triboelectric nanogenerator (TENG) provides an effective method to harvest mechanical energy from the environment. The morphology and structure of frictional electrode materials of this type of device affect the output performance significantly. Metal–organic coordination polymers (CPs) with special structure advantages offer a vast pool of materials enabling high performances. Two Co-CPs based on terephthalic acid and 2,5-dihydroxyterephthalic acid ligands, respectively, were used to fabricate TENGs. Detailed electrical characterizations of the TENG devices revealed that the introduction of the substituent groups in the organic ligands leads to the structural changes of CPs, which ultimately leads to significant differences in the output performance.