By employing the pyridinium hexafluorophosphate task-specific ionic liquids 1-butyl-4-methylpyridinium hexafluorophosphate ([C4mpyr][PF6]) and 1-ethylpyridinium hexafluorophosphate ([C2pyr][PF6]) as the reaction medium, mineralizer, structure-directing agent, and, in the case of the smaller pyridinium cation, even a structural component, it was possible to obtain five new alkali metal iron phosphates featuring interconnected FeX6 octahedra and PX4 (X = F, O, or OH) tetrahedra. NaFe(PO3F)2 (1) is a dense 3D structure, RbFe(PO3F)(PO2(OH)F)(PO2(OH)2) (2) features 1D strands, (C2pyr)LiFe(PO3F)3(PO2F2)F (3) has 2D layers, and LiFe(PO3F)(PO2F2)F (4) as well as Cs0.75Fe(PO2.75(OH)0.25F)(PO2F2)2 (5) are 3D open frameworks. While in 1-2 as well as in 4 and 5, FeX6 octahedra and PX4 (X = F, O, or OH) tetrahedra alternate, 3 features octahedra dimers, Fe2X11 (X = F, O, or OH). The magnetic behavior of all compounds is governed by antiferromagnetic interactions. Interestingly, 3 exhibits a broad maximum in the temperature dependence of the magnetic susceptibility, characteristic of a low-dimensional magnetic system consistent with the presence of Fe-Fe dimers in its crystal structure.