Ligand-capped lanthanide-doped fluoride nanocrystals have been prepared and fully characterized. Organic ligands can be used to promote efficient sensitization of lanthanide luminescence in the fluoride matrix up to a 330-fold enhancement in intensity, and to provide sizeable quantum yields of luminescence. The variation of luminescence efficiency in the capped nanocrystal series can be straightforwardly correlated to the energy of the measured ligand triplet states. The intense luminescence emission of most of the systems renders them very attractive for optical applications. © 2013 Springer Science+Business Media Dordrecht.