The hydrothermal synthesis, crystal structure and some properties of a zinc phosphite with a neutral cluster, [Zn(2,2′-bipy)] 2 (H 2 PO 3 ) 4 , are reported. This compound crystallizes in the triclinic system of space group P-1 (No. 2), a=8.3067(5) Å, b=8.9545(4) Å, c=10.0893(6) Å, α=95.448(2)°, β=99.7530(10)°, γ=103.461(2)°, V=712.23(7) Å 3 , Z=1. The cluster consists of 4-membered rings formed by alternating ZnO 3 N 2 square pyramids and H 2 PO 3 pseudo pyramids, with two “hanging” H 2 PO 3 groups attached to each of the Zn centers. The clusters are linked together by extensive multipoint hydrogen bonding involving the phosphite units to form a sheet-like structure. This compound represents the first example of zinc phosphite with POH bonds. An intense photoluminescence was observed from this compound upon photoexcitation at 388 nm.