Four Dy(III) and Zn/Ni-Dy(III) complexes with polyamine phenol ligand were synthesized and structurally characterized, namely [Dy(CH3OCH3)L] (1), [Dy-2(mu-H2O)L-2] (2), [Zn2DyL2]ClO4 center dot H2O (3) and [Ni2DyL2]ClO4 center dot H2O (4) (H3L=N,N',N ''-tris(3,5-dimethyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). X-ray crystallographic analysis reveals that 1 and 2 take mononuclear and binuclear structures, respectively, and both 3 and 4 take binuclear M-Dy(III)-M structures (M=Zn (3), Ni (4)). Magnetic measurements showed that complexes 1 and 2 exhibited field-induced slow magnetic relaxation behaviours, while 2 had multiple magnetic relaxation processes. However, no obvious slow magnetic relaxation behaviors were observed in 3 and 4. Fluorescence analyses reveal that complexes 1 similar to 3 have narrow-band characteristic emissions of Dy(III) ions, but no significant emission was observed in 4 because of the fluorescence quenching effect of Ni(II) ions. CCDC: 1849452, 1; 1849454, 2; 1849453, 3; 1943989, 4.