A new kind of supramolecular building unit was synthesized from 1,2,4,5-benzenetetracarboxylic acid and 4-hydroxypyridine by a simple procedure. The structure of the building unit was characterized by H-1 NMR spectroscopy, IR spectroscopy, EA, and XRD. Under suitable conditions, supramolecular hydrogels and fibers were formed from the building unit through hydrogen bonds between the donors and acceptors.