A strong green-light-emitting Tb complex [Tb₂(csal) ₆(H₂O)₄]·4H₂O (1) (Hcsal = 4-chlorosalicylicacid) has been synthesized. The structure was determined by single crystal X-ray diffraction. 1 exhibits a discrete dinuclear structure which is further assembled into a 3D supramolecular network by hydrogen bonding and aromatic π-π stacking interactions. This complex was used to detect ethylenediamine (EDA), triethylamine (TEA) and ethanolamine (EOA), the relationship between luminescence intense of 1 and concentrate of EDA or TEA can be fitted in Stern-Volmer equation. The results indicate that 1 is a promising probe for detecting amines with high selectivity and sensitivity.