Sodium chloride (NaCl) is the main constituent of sea-salt aerosols. During atmospheric transport, seasalt aerosols can interact with gases and other particles including secondary aerosols containing ammonium sulfate ((NH4)2SO4). This paper reports on the deliquescence relative humidity (DRH) of internally mixed sodium chloride–ammonium sulfate (NaCl/(NH4)2SO4) coarse particles by means of an acoustic levitation system fitted with a confocal Raman microscope (CRM). The chemical composition and physical state of individual levitated particles of different initial NaCl mole fractions were monitored during the deliquescence cycle by CRM. Experimental results were compared to the data predicted by the thermodynamic model E-AIM (Extended-Aerosol Inorganics Model). We demonstrated that NH4Cl, Na2SO4 and NH4NaSO42H2O are formed in recrystallized particles and coexist with NaCl and (NH4)2SO4. All these products are randomly distributed within the particles. Deliquescence curves described two or three-stage phase transitions depending on the initial composition of the droplet. Significant discrepancies between the model and the laboratory experiments were observed for NaCl mole fractions varying between 0.40 and 0.77 due to a divergence between the predicted and the truly present products in the particles’ solid fraction during the humidification cycle.