A 3D chiral cobalt phosphonate has been obtained from achiral precursors in the absence of chiral inducers. Remarkably, the bulk sample is largely enantio-enriched with particular handedness through symmetry-breaking crystallization in spite of multiple repeated experiments. Moreover, protonation of this chiral material introduces Bronsted acid sites, the structure of which is unique to the heterogeneous phase for the ring opening of epoxies.