Dust storms in arid regions transport desert salts and dust, affecting geochemical processes, atmospheric chemistry, climate, and human health. This study examines how the gas–salt interface composition of desert salt changes with varying relative humidity (RH), using ambient pressure X-ray photoelectron spectroscopy (APXPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and molecular dynamics (MD) simulations. Ion chromatography analysis of desert salt indicates it is predominantly composed of sulfate, sodium, and magnesium ions, with traces of calcium, chloride, nitrate, and potassium ions. APXPS and NEXAFS surface analyses show that, at 0% RH, the gas–salt interface primarily features Na₂SO₄, with smaller amounts of MgSO₄ and a trace of NaCl on the top layers. As humidity increases, the composition at the gas–salt interface changes, notably with Mg²⁺ binding to SO₄^2– ions and a dominant NaCl formation throughout the studied surface depth. This shift indicates a transition from a sulfate- to a chloride-rich surface as humidity increases, contradicting MD simulations that predicted that on salt crystals covered by a submonolayer of water with electrolytes, chloride ions migrate toward the liquid–solid interface. This discrepancy indicates that other factors, like enhanced ionic mobility at grain boundaries, might drive the accumulation of chloride ions at the gas interface. The study emphasizes the crucial role of adsorbed water in ion migration and surface composition transformation of desert salts, affecting geochemical processes in arid regions.