Copper(II) complexes constructed from enantiopure Schiff‐base ligands derived from o‐vanillin and methionine or from their racemic mixture have been employed as metalloligands towards mercury(II) ions. The nature of the heterometallic CuII‐HgII complexes (coordination polymers or oligonucler species), resulted from the reactions of the copper(II) complexes with HgCl2 or HgI2, is different. The enantiopure metalloligands lead to chiral coordination polymers, 1∞[{Cu(R‐/S‐valmet)(H2O)}2HgCl2]·5H2O·CH3OH and 2∞[{Cu2(R‐/S‐valmet)2(μ‐H2O)(H2O)2}HgI2]·4H2O. The reaction of the racemic mixture of the metalloligands with HgX2 affords discrete complexes: [{Cu(R,S‐valmet)(H2O)2}2HgCl2]·2H2O and [{Cu(R,S‐valmet)(H2O)(CH3OH)}2Hg2I4].