The improvement of fluorite quality is an attractive measure to recover fluoride from high F⁻ content wastewater and thus reduces the fluorite sludge generation rate, and the removal of contaminant pollutants could be helpful for the production of ceramic grade fluorite (>85%). In this work, typical etching wastewater was collected and characterized, and SO₄²⁻ was found to be the main barrier for high quality CaF₂ production, while CaSO₄ could also contribute to CaF₂ precipitation. The optimum SO₄²⁻ content was adjusted by the introduction of barium salts, to keep a balance between the CaF₂ quality and the settlement process. The ceramic grade CaF₂ of 88% was obtained under the conditions: [Ca]/[F] of 1.29, pH 8.14 and C_sulfate of 117.4 mg L⁻¹. The residual SO₄²⁻ content should be kept in the range of 100–130 mg L⁻¹, and the formation of CaSO₄, combined with CaF₂ could accelerate the CaF₂ precipitation by the co-precipitation method, with a larger particle size from 758 nm (without SO₄²⁻) to 898 nm. The gradient settlement of CaF₂ contributes to the recovery of fluoride from etching wastewater, while CaF₂ preparation should be carried out in a dynamic experiment, such as a fluidized bed, for further research.