Ionic species can be stabilized in the water core of a water-in-CO2 microemulsion in supercritical fluid CO2; by mixing two microemulsions containing Ag+ and X− ions separately, silver halide (AgX) nanoparticles were synthesized in supercritical CO2; the water-in-CO2 microemulsion may provide a reaction system for a wide range of nanoparticle syntheses involving ionic species in supercritical CO2.