A series of the arsenate-substituted natroalunite solid solutions were synthesized by hydrothermal precipitation at 200 °C and pH of 4 and characterized to investigate the AsO₄ substitution for SO₄ in natroalunite as the base of a possible immobilization method for arsenic. The AsO₄ substitution in natroalunite increased when the [AsO₄/(AsO₄ + SO₄)]_aq molar ratios of the initial aqueous solutions increased and the maximum substitution reached ~67% molar for the [AsO₄/(AsO₄ + SO₄)]_aq = 0.26. The XRD analysis confirmed that all hydrothermal synthetical solids for the [AsO₄/(AsO₄ + SO₄)]_aq ≤ 0.26 were characteristic of natroalunite-type phases. The AsO₄ substitution in the natroalunites increased the c lattice parameters, owing to the difference between the SO distance and the AsO distance in the crystal structures. For the [AsO₄/(AsO₄ + SO₄)]_aq = 0.28 at 200 °C and pH of 4, a mixture of natroalunite, amorphous arsenate phase and Na₂SO₄ was formed. The crystals of the arsenate-substituted natroalunites were regular ditrigonal scalenohedron (pseudo-octahedron). The Raman spectra were characterized by two bands centered upon 899–917 cm⁻¹ and 981–997 cm⁻¹, which represented the symmetric stretching vibration v₁(AsO₄) and the antisymmetric stretching vibration v₃(AsO₄), respectively. The infrared bands around 868–897 cm⁻¹ were assigned to the symmetric stretching vibration v₁(AsO₄). The thermal decomposition of the arsenate-substituted natroalunites showed three separated endothermic steps, namely the loss of H₃O⁺, the loss of OH⁻ and the loss of SO₃ + (As₂O₃ + O₂). The solubility products [K_sp] and the Gibbs free energies of formation [ΔG_f^o] for the arsenate-substituted natroalunites decreased from 10^−81.21 to 10^−109.16 and from −4714.49 kJ/mol to −5352.95 kJ/mol with the increase of the AsO₄ substitution from 0% to 67%, respectively.