Metal-organic frameworks (MOFs) are an emerging class of catalysts that posess large surface area due to intrinsic porosity, and high metal loading. However, they often lack catalytic properties due to the saturated coordination sphere of metal centres. Some MOFs have been found to exhibit good to excellent catalytic activity in a limited number of reactions, resulting from solvent induced changes of the coordination sphere. In this work the coordination sphere changes of Cu(bpy)(H2O)(2)(BF4)(2)(bpy) (bpy = 4,4-bipyridine) affected by common solvents with different dipole moments were studied by means of solution-state H-1 and F-19 NMR. It was found that organic molecules interact with the copper(II) centre and cause structural transformations of Cu-MOF in proportion to both the dipole moment and concentration of solvent. The sensitive NMR resonances reveal an exchange of the BF4 anions to DMSO (dimethylsulfoxide) molecules at axial positions of Cu(II) and even breakage of Cu-N and Cu-O bonds in equatorial positions with increasing DMSO concentration. Therefore, solvents with suitable dipole moments (1.7-3.9) can promote structural changes and, thus release highly active sites in the reaction, which can efficiently enhance the activity of Cu-MOF catalysts.