Metal-center-driven spontaneous resolution of a chiral coordination polymer, [Ni(SDB)(BIX)](n) (1), from achiral precursors has been probed by single-crystal X-ray diffraction and circular dichroism spectroscopy. Enantiomorphs 1P and 1M showed a parallel interpenetrated 2D -> 3D chiral framework with (8(2).10) topology. Switching of the metal center under the same reaction parameters resulted in isostructural achiral and noninterpenetrating (4,4) grid-type sql networks [M(SDB)(BIX)](n), where M = Co-II, Zn-II, and Cd-II for 2-4, respectively.