The Mn-2(HPO3)F-2 phase has been synthesized as sing e crystals, by using mild hydrothermal conditions. The compound crystallizes in the orthorhombic Pnma space group, with unit cell parameters of a = 7.5607(8), b = 10.2342(7), and c = 5.5156(4) angstrom, with Z = 4. The crystal structure consists of a three-dimensional framework formed by alternating (010) layers of [MnO3F3] octahedra linked up by three connected [HPO3] tetrahedra. Luminescence measurements were performed at different temperatures between 10 and 150 K. The 10 K emission spectrum of the octahedrally coordinated Mn(II) cation exhibits a broad band centered at around 615 nm corresponding to the T-4(1) -> (6)A(1) transition. In order to explore the effect of the Mn(II) concentration and the possibility of enhancing the luminescence properties of the Mn(II) cation in Mn-2(HPO3)F-2, different intermediate composition members of the finite solid solution with the general formula (MnxZn1-x)(2)(HPO3)F-2 were prepared and their luminescent properties studied. The magnetic and specific heat behavior of M-2(HPO3)F-2 (M = Mn, Fe) have also been investigated. The compounds exhibit a global antiferromagnetic ordering with a spin canting phenomenon detected at approximately 30 K. The specific heat measurements show sharp lambda-type peaks at 29.7 and 33.5 K for manganese and iron compounds, respectively. The total magnetic entropy is consistent with spin S = 5/2 and S = 2 of Mn(II) and Fe(II) cations.