The structural, thermodynamic, and magnetic properties of Na₂CrCl₄ have been investigated to provide fundamental insights into this ternary halide relevant to chloride-based molten salt reactor systems. Room-temperature powder X-ray and neutron diffraction confirm a monoclinic (P2₁/c) structure and phase purity. Neutron diffraction measurements at 4.6 K reveal additional magnetic reflections indexed with (Formula presented), indicating the onset of long-range antiferromagnetic order. Low-temperature heat capacity measurements in the range 2–300 K show a pronounced λ-type anomaly at T_N = 8.5 ± 0.5 K, with an associated magnetic entropy S_mag = 11.9 ± 0.4 J K^–1 mol ^–1 consistent with antiferromagnetic ordering of high-spin Cr²⁺ (S = 2), a second-order phase transition. The standard molar entropy at 298.15 K, S_m^°(298.15 K) = 256.8 ± 7.7 J K^–1 mol ^–1, is slightly lower than previous CALPHAD assessments of the NaCl-CrCl₂ system. Magnetic susceptibility measurements also confirm antiferromagnetic behavior, with a Curie–Weiss fit giving μ_eff = 5.57 ± 0.05 μ_B and θ_CW = −15.0 ± 1.0 K. Compared to the related ferromagnetic chlorides K₂CrCl₄, Rb₂CrCl₄, and Cs₂CrCl₄, Na₂CrCl₄ exhibits a distinctly lower ordering temperature and antiferromagnetic structure, likely due to variations in lattice geometry and exchange interactions. These results provide the first experimental thermodynamic parameters for Na₂CrCl₄, contributing to refining phase diagrams and corrosion models in chloride salt systems. ... Read more