Piperazine (PRZ) and ligustrazine (TMP) were respectively in combination with protocatechuic acid (PA) to form complexes I and II. The structures of complexes I and II were confirmed by H-1 NMR, C-13 NMR, and single crystal X-ray diffraction. The effects of PA and its complexes on chondrocytes growth were measured using the MTT assay. Furthermore, the anticoagulant activities of PA and two complexes were evaluated by four coagulation assays (PT, APTT, TT, and FIB). This study indicates that concurrently using PA and TMP may have novel therapeutic uses in age-related disorders such as osteoarthritis and cardiovascular disease.