Under ambient conditions or 160◦C, two supramolecular isomers, namely [(H4PTTA)(H2O)2 (DMF)] and [(H4PTTA)(H2O)3 ]··Guest (1-L and 1-H, H4PTTA = N-phenyl-N′-phenyl bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide tetra-carboxylic acid, Guest = DMF and H2O), were obtained through the reaction of H4PTTA in a mixture of H2O and dimethylformamide. The single crystal structures reveal the temperature-dependent supramolecular isomerism derived from the torsion of semi-rigid of H4PTTA. The 1-L prepared at room temperature is a hydrogen bond base...