A water-stable homochiral luminescent metal-organic framework (HLMOF), {[Cd(l)(4,4'-bipy)]·DMA·5H2O}n (1), was obtained by a spontaneous symmetry-breaking crystallization from achiral precursors without any enantiopure auxiliary. The homochirality of 1 was confirmed by single-crystal X-ray diffraction and CD spectroscopy. Complex 1 exhibits an interesting enantioselective sensing of d/l-penicillamine in water.