Two organic–inorganic hybrid salts, tris(2-amino-4,6-dimethylpyridinium) tris(oxalato)ferrate(III), (C7H11N2)3[Fe(C2O4)3] (1), and tris(4-dimethylaminopyridinium) tris(oxalato)ferrate(III) tetrahydrate, (C7H11N2)3[Fe(C2O4)3]·4H2O (2), have been synthesized and characterized by elemental and thermal analyses, IR spectroscopy, single-crystal X-ray diffraction, and SQUID magnetometry. Compounds 1 and 2 crystallize in triclinic P-1 and monoclinic C2/c space groups, respectively. Each compound contains the anionic complex [Fe(C2O4)3]3- in which the central metal is six-coordinate in a slightly distorted octahedron defined by three chelating oxalate(2-) ligands. The two substituted pyridinium cations are isomers. However, due to the great steric hindrance provided by the bulky cation, 2-amino-4,6-dimethylpyridinium, only the 4-dimethylaminopyridinium cation, the smallest of this series, led to formation of 2 with enough vacant spaces to be occupied by four solvent water molecules. In the crystals, cations and anions are connected via hydrogen-bonds of the types N–H⋯O in 1 and N–H⋯O and O–H⋯O in 2, with π–π stacking interactions between the pyridine rings stabilizing the 3-D framework. The thermal studies confirmed the anhydrous character of salt 1 and the presence of water molecules in salt 2. The magnetic susceptibility measurements in the 2–300 K temperature range revealed weak antiferromagnetic coupling in the two salts.