A centipede like thiocyanate-bridged multi-nuclear copper(I/II) complex, [Cu2L(CH3OH)(NCS)3]n, derived from 2-(((2-(dimethylamino)ethyl)imino)methyl)-5-fluorophenol (HL), was prepared and characterized by elemental analysis, IR and UV–vis spectra, as well as single crystal X-ray diffraction. The Cu1 ion in the +2 oxidation state is coordinated by the tridentate Schiff base ligand in a square pyramidal geometry, with the other two sites occupied by one N atom of the thiocyanate ligand and one methanol O atom. The Cu2 ion in the +1 oxidation state is coordinated by one N and three S atoms from four thiocyanate ligands, forming a tetrahedral geometry. The CuI ions are linked by thiocyanate ligands to form a one-dimensional chain with [CuI 2(μ 1,3,3-NCS)2] as the repeat unit. The [CuIIL(CH3OH)] moieties are linked to the chain through thiocyanate ligands. The complex has remarkable inhibitory activity on Jack bean urease with an IC50 value of 1.3 μmol L–1.