The mixed-valence Fe^IIFe^III 2D coordination polymer formulated as [TAG][Fe^IIFe^III(ClCNAn)₃]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn^2– = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [Fe^IIFe^III(ClCNAn)₃]⁻ establish in the ab plane, with an intralayer metal–metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe–O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C₃ symmetry to the structure and engages in intermolecular N–H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10^–3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type Fe^IIFe^III 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.