The complex fluoride BaLiF3 and BaLiF3∶Ce3+ nanocrystals were synthesized in cetyltrimethylammonium bromide(CTAB)/2-octanol/water microemulsion systems.XRD analysis shows that the products were single phase and XPS analysis shows the oxygen content was low.The result of ESEM confirms that the average size of the BaLiF3 nanocrystals was 28 nm in diameter.The emission peak of the BaLiF3∶Ce3+ nano-particles synthesized by microemulsion shows obvious blue shift in comparison with that of BaLiF3∶Ce3+ synthesized by the reaction at a high temperature and full width at half maximum(FWHM) of emission band was broaden.