A dynamic combinatorial library (DCL) is a set of molecular species existing in equilibrium in solution that can undergo self-assembly via reversible chemical bonds. Here, we report a unique DCL system that shows the independent crystallization of products from solvents with slightly different polarities. The reaction of a 1:1 mixture of [Au-2(dppm)(DL-cys)(2)](2-) and [Au-2(dppm)(DL-pen)(2)](2-) with Ni2+ in solution gave a DCL containing 10 cyclic (Au2NiII)-Ni-I molecules of [Au2Ni(dppm)(DL-cys/DL-pen)(2)]. Upon crystallization, three kinds of enantiomeric pairs, homoleptic-heterochiral C/A-[Au2Ni(dppm)(D-cys)(L-cys)], homoleptic-homochiral [Au2Ni(dppm)(D-pen)(2)]/[Au2Ni(dppm)(L-pen)(2)], and heteroleptic-homochiral [Au2Ni(dppm)(D-cys)(D-pen)]/[Au2Ni(dppm)(L-cys)(L-pen)], were produced from the reaction solutions of MeOH, MeOH/H2O, and EtOH/H2O, respectively. The independent crystallization was explained by a combination of the different hydrogen-bonding interactions of the (Au2NiII)-Ni-I molecules in the crystal and the different thermodynamic stabilities of the molecules in solution.