Making use of the multifunctional properties of ionic liquids by employing them as a fluoride resource and hydrophilic phase, we have grown small, monodisperse, highly luminescent Ln3+-doped NaGdF4 nanorods at the interface between octadecene and the reactive ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. The obtained nanocrystals could further be endowed with functional groups and rendered water dispersible, which allows them to be used for biodetection.