Abstract: An organic–inorganic hybrid zinc phosphate with 28-ring channels was synthesized by use of an organic ligand instead of organic amine template under a hydro(solvo)thermal condition. This crystalline zinc phosphate contains large channels constructed from 28 zinc and phosphate tetrahedral units. The walls of the channels consist of two types of zincophosphate chains, in which the Zn atoms are coordinated by 2,4,5-tri(4-pyridyl)-imidazole ligands as pendent groups. This compound exhibits yellow emission and interesting properties of removing cobalt, cadmium, and mercury cations from aqueous solution. A new two-dimensional organic–inorganic hybrid zincophosphate was also obtained by changing the solvent mixture ratios in the synthesis.