Employing achiral organic amines (2-methylbenzimidazole and 1,4-diazabicyclo[2.2.2]octane) as the structure-directing agent and ligand, two chiral zincophosphites, [Zn(C(8)H(8)N(2))(HPO(3))] 1 and (C(6)H(13)N(2))[Zn(3)(C(6)H(12)N(2))(HPO(3))(3)(H(2)PO(3))] 2, have been hydro(solvo)-thermally synthesized, crystallizing in the chiral space group P2(1)2(1)2(1). Single-crystal structural analysis reveals that compound 1 consists of alternating ZnO(3)N and HPO(3) units exhibiting a neutral one-dimensional chiral chain. Interestingly, the organic ligands interact with the inorganic chain via hydrogen-bonds in hydrogen-bonded helix fashion. Compound 2, a three-dimensional chiral open framework with 16-MR channels, is formed by the distorted {Zn(3)P(4)} secondary building unit (SBU). The organic amine molecules play dual roles as both ligands and countercations.