An alpha-quartz-mimetic chiral coordination network of [Ag(L-1)(CF3-SO3)](n) (L-1 = 5,5'-bipyrimidine), after treatment with PF6- anions, undergoes a solution-state structural transformation toward [Ag-(L-1)(PF6)](n) with a cristobalite-mimetic chiral structures. This structural transformation is accompanied by substantial enhancement in the fluorescent intensity and in the second-harmonic-generation response. The results also demonstrate an effective design strategy based on the spontaneous resolution route for the preparation of chiral architectures.