A new framework cobalt(II) hydroxyl phosphate, Co2PO4OH, was prepared by ionothermal synthesis using 1-butyl-4-methyl-pyridinium hexafluorphosphate as the ionic liquid. As the formation of Co2PO4F competes in the synthesis, the synthesis conditions have to be judiciously chosen to obtain well-crystallized, single phase Co2PO4OH. Single-crystal X-ray diffraction analyses reveal Co2PO4OH crystallizes with space group I4(1)/amd (a = b = 5.2713(7) angstrom, c = 12.907(3) angstrom, V = 358.63(10) angstrom(3), and Z = 4). Astonishingly, it does not crystallize isotypically with Co2PO4F but rather isotypically with the hydroxyl minerals caminite Mg-1.33[SO4(OH)(0.66)(H2O)(0.33)] and lipscombite Fe2-yPO4(OH) (0 <= y <= 2/3). Phosphate tetrahedra groups interconnect four rod-packed face-sharing (1)(infinity){CoO6/2} octahedra chains to form a three-dimensional framework structure. The compound Co2PO4OH was further characterized by powder X-ray diffraction, Fourier transform-infrared, and ultraviolet-visible spectroscopy, confirming the discussed structure. The magnetic measurement reveals that Co2PO4OH undergoes a magnetic transition and presents at low temperatures a canted antiferromagnetic spin order in the ground state.