Monodispersed CaF2:Yb3+/Er3+ nanocrystals have been prepared via a facile wet chemical technology. The upconversion luminescence properties of CaF2:Yb3+/Er3+ nanocrystals were compared with those of NaYF4:Yb3+/Er3+ nanocrystals with different phases and particle sizes. The results indicated that CaF2 is a promising host material for producing desirable upconversion luminescence.