An open-framework zinc-cobalt phosphate CoZnPO 4 -V with 16-ring extra-large-pore channels has been obtained in the presence of chain-type polyamines as the structure directing agent (SDA). Its large single crystal suited for structure refinement has been prepared with the assistance of small organic amines. Single-crystal X-ray diffraction analysis has shown that CoZnPO 4 -V is a novel metal phosphate. It crystallizes in monoclinic space group P2 1 /c (No. 14), with a = 31.936(3) Å, b = 8.3775(7) Å, c = 15.7874(13) Å, α = γ = 90°, β = 97.0530(10)°, V = 4191.8(6) Å 3 , and Z = 4 with R 1 = 0.0455，wR 2 = 0.0869. Its three-dimensional framework can be considered as stacking from two-dimensional nets and onedimensional units as linkers. Between the stacking nets and linkers are located extra-large channels with 16-ring apertures.zinc-cobalt phosphate, chain-type polyamines, structure directing agent, small organic amine