Two new temperature-controlled coordination polymers, {{Ag-2.67[(1R,2R,(NS)-S-1,(NS)-S-2)-4-bpcd](2)}center dot 2.67ClO(4)center dot 1.33H(2)O}(n) (1) and {{Ag[(1R,2R,(NS)-S-1,(NS)-S-2)-4-bpcd]}center dot ClO4 center dot H2O}(n) (2) [(1R,2R)-4-bpcd = (1R,2R)-N-1,N-2-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine], with congenital chiral centers from the ligand and acquired chiral centers formed by the coordination interaction, have been synthesized via a chiral multidentate organic bridging ligand, in which 1 displays a chiral (6,3) network, while 2 has a (4,4) topology. Circular dichroism (CD) spectra confirmed that the bulk samples are chiral. The frameworks have potential as multifunctional materials due to their luminescent and nonlinear optical (NLO) properties. The present study demonstrates that reaction temperature is a crucial factor for the construction of coordination polymers.