Nanostructured metal fluorides (nanofluorides) are an emerging type of inorganic nanocrystals (NCs) with unique physiochemical properties for advanced applications. One recent demonstration used water-dispersed ultrasmall CaF 2 nanofluorides as imaging agents that combined the advantages of inorganic NCs with the benefit of background-free 19 F-magnetic resonance imaging ( 19 F-MRI). Nevertheless, obtaining small nanofluorides with a face-centered cubic crystal structure, where all fluorides are magnetically equivalent to result in a single 19 F NMR signal, is challenging for other types of nanofluorides, preventing their use in 19 F-MRI. Here, we show the development of ultrasmall, waterdispersed, barium fluoride (BaF 2 ) NCs for bioimaging applications. By doping BaF 2 with two types of lanthanides, diamagnetic-La 3+ and paramagnetic-Sm 3+ , we were able to control the morphology and 19 F-MR properties of the final La,Sm:BaF 2 (termed LaSamBa) formulation. The fine-tuning of the La 3+ content enabled us to obtain monodispersed 4.5 nm NCs, and control over the Sm 3+ content provided LaSamBa with very short T 1 relaxation properties (ca. 100 ms) needed for enhanced 19 F-MRI sensitivity. This type of nanofluorides was examined in two different imaging modalities (i.e., 19 F-MRI and CT), benefiting from their single 19 F-NMR signal and the high atomic number of barium atoms, respectively. As their 19 F chemical shift significantly differs from that of other nanofluorides (e.g., CaF 2 and SrF 2 ), LaSamBa expanded the nanofluoride library for future multitarget 19 F-MRI studies.