The hydrogen-bonded organic framework (PFC-32), constructed by tetrahydroxyquinone (THQN) and diethylamine (DEA), was readily prepared via hydrothermal synthesis in DEF (N,N-diethylformamide). PFC-32 was characterized by PXRD, IR, UV-Vis, TGA and photoluminescence (PL). Single crystal analysis reveals that PFC-32 shows a three-dimensional (3D) framework, where the THQN anions are coplanar and separated by DEA cations. PFC-32 displays intrinsic photoluminescence property owing to the alleviation of the aggregation-caused quenching (ACQ) effect caused by π-π stacking.