Two new 1D polymeric heterometallic copper–vanadium compounds were prepared. The polymers are constructed from [Cu(im)4]2+ cations that are coordinated to two terminal oxido ligands of [V2O4(mand)2]2− anions. The stronger coordination in [Cu(im)4V2O4(mand)2]n (1) that contains the racemic mandelato ligand is manifested by a shorter Cu‒O bond distance 2.4095(12) Å, while the weaker interaction in [Cu(im)4(V2O4((S)-mand)2)]n·2nH2O (2) is exhibited by Cu‒O bond distances 2.4547(16) Å and 2.5413(16) Å. The vanadate anion in compound 2 carries only the (S)-enantiomer of the initial mandelic acid and differs from the anion in 1 in parallel cis orientation of the phenyl groups of the mandelato ligand. FT-IR spectroscopy was used for the confirmation of the coordination mode of mandelato ligand. Strong bands corresponding to the vibrations of carboxyl groups can be observed around 1650 and at 1344 cm−1. The stretching vibration of deprotonated hydroxyl group in the mandelato ligand occurs at 1045 and 1065 cm−1 for 1 and 2, respectively. In addition, the very strong, characteristic band corresponding to ν(V=O) vibration can be observed at 931 cm−1 for 1 and 925 cm−1 for 2, as well as in Raman spectrum.