A large pore, zeolitic nickel(II) phosphate, VSB-5, has been prepared under hydrothermal conditions (6 days, 180 degreesC, augenous pressure). Its unit cell is hexagonal with the following parameters a = 18.209(1) Angstrom, c = 6.3898(7) Angstrom, V = 1834.7(3) Angstrom (3) and die space group is P6(3)/m Its structure was solved ab initio from conventional X-ray powder diffraction data. It is built from tunnels along c axis, delineated by 24 NiO6 polyhedra, with a free diameter estimated to ca. 10 Angstrom. It could also be described in terms of pillared building units where the central, half occupied ND octahedra are face sharing. Ni2 octahedra and phosphate groups make the connection between Ni3 and Ni1 octahedra by sharing edges and faces, and corners, respectively. The SBU are then connected by sharing corners directly between Ni1 and Ni2 octahedra and via phosphate groups to form the 3D framework. 6 SBU are needed to form a ring. Temperature dependant X-ray diffraction has shown that VSB-5 was stable to about 425 degreesC. The structure then collapses to form an amorphous phase and recrystallizes to form condensed Ni-3(PO4)(2) at above 750 degreesC. It becomes microporous on calcination in air at 350 degreesC, yielding a BET surface of 320 m(2).g(-1).