The influence of ω 0, the mole ratio of water-to-surfactant content ([H2O]/[surfactant]), on the crystal size of calcium carbonate (CaCO3) produced by reaction crystallisation in microemulsion systems was investigated. Crystallisation was induced by the reaction between an aqueous solution of sodium carbonate and water in oil micellar solutions of calcium chloride stabilised by cationic surfactant cetyltrimethylammonium bromide and cosurfactant n-butylalcohol. The X-ray diffraction results showed that calcite is the main state of CaCO3 crystal when ω 0 >30, but because of the stable reverse micelles system, vaterite was the predominant crystal form when ω 0 < 30. Scanning electron microscopy and high-resolution transmission electron microscopy results showed spherical CaCO3 nanoparticles obtained with narrow size distribution, and with the ratio of water-to-surfactant increasing from 3.40 to 22.63, the particles size increased from 15 to 70 nm. The influence of ω 0 on the crystal size and morphology of CaCO3 was very clear.