Highly dispersible Tm3+/Yb3+-doped LiYF4 nanocrystals were synthesized using a thermal decomposition method. Upon excitation with a NIR diode laser (980nm), the dilute dispersion of the nanocrystals exhibits several strong emissions in regions spanning the deep-UV to NIR, all originating from a single dopant/sensitizer (Tm3+/Yb3+) combination. The material is envisioned to have potential interest in anti-counterfeiting, biomedicine and solution-based scintillation applications.