A neutral metal-organic framework [CoNa3(1,2,3-Hbtb)(1,2,3-btb)] (1) has been synthesized through an ionothermal method using 1-ethyl-3-methylimidazolium bromide as solvent (1,2,3- H3btb=1,2,3-benzenetricarboxylic acid). The complex has been characterized by IR spectroscopy, elemental analysis, PXRD and single-crystal X-ray diffraction. The structure of 1 exhibits a layer network structure in which Co(II) is five-coordinated forming a distorted trigonal bipyramid. Na1 and Na3 are surrounded by seven oxygen atoms, and Na2 is six-coordinated. In the structure, the anions of 1,2,3-H3btb are embedded in two bridging μ8 coordination modes. The luminescence properties of 1 have been investigated in the solid state at room temperature.