The upconversion (UC) emission intensity of Ln3+-doped CaF2 nanomaterials is not ideal, which limits their application in some advanced scientific fields. Hence, it is extremely imperative to enhance the emission intensity of UC nanocrystals. In this work, an ionic-liquid-assisted hydrothermal method based on an ethylene glycol (EG) and ionic liquid (IL) two-phase system was used to synthesize CaF2 doped with Yb3+ and Ho3+. The influence of the amount of IL and the reaction time as well as the concentration of Gd3+ doping on morphology and size was studied in detail, and the growth mechanism was proposed. Green UC luminescence materials were obtained through co-doping Yb3+ and Ho3+ ions. Furthermore, the luminescence of UC was increased monotonically with the introduction of Gd3+ ions. The effect mechanism of Gd3+ doping on the UC luminescence was put forward, which might provide a new method for the promotion of UC luminescence. In addition, the temperature sensing of CaF2: Yb3+/Ho3+/Gd3+ was investigated, which demonstrated that the phosphor has a potential application prospect in thermal sensing. Meanwhile, CaF2: Yb3+/Ho3+/Gd3+ also exhibited a paramagnetic property at room temperature. Therefore, these multifunctional nanocrystals may have prospective applications in optical bioimaging, magnetic resonance imaging, and temperature sensing.