Effects of the basicity and the CaF2 content on viscosity of CaF2–CaO–SiO2 slag with high CaF2 content for electroslag remelting process were investigated by the rotating cylinder method in the temperature ranging from 1773 to 1533 K. The relationship between the structure and the viscosity variation of the slag was also clarified by the Fourier transform infrared (FT-IR) spectroscopy of water-quenched slags. The results show that the viscosity gradually decreases with the increase in the basicity of the slag from 1 to 3 under the present experimental conditions. It is found that the CaO does not depolymerize all silicate complex anions for the slag with the basicity of 1 at 1773 K and there are still some bridging oxygens. With the increase in the basicity to 3, the silicate complex anions are almost completely depolymerized to simple ions. As the CaF2 content increases from 40 to 80 mass%, the viscosity of the slag decreases due to the dilution of CaF2 for the concentration of the silicate complex anions in unit volume of the slag. Moreover, the effect of the temperature on the viscosity is not remarkable. The activation energy of viscous flow exhibits the decrease from 40.4 to 26.7 kJ · mol−1 with the increase in the basicity from 1 to 3, and also the decrease from 66.6 to 31.0 kJ · mol−1 with the increase in the CaF2 content from 40 to 80 mass%.