Insulating ceramics with anorthite and diopside as the main crystal phases were manufactured using phosphate tailings, coal gangue, and quartz as raw materials, which were fired at 1160–1190 °C for 2 h. The structure and micromorphology of the samples were investigated using X-ray diffraction, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. Dense ceramic samples exhibited an apparent porosity of less than 0.3%, densities of 2.64–2.86 g/cm3, bending strength of 127.71–172.73 MPa, dielectric constants of 6.98–7.79, and dielectric losses of 0.0086–0.0024 at 20 °C and frequency of 1 MHz. The effects of impurity elements on ceramic properties are determined. The excellent electrical properties can be attributed to the solid solution of iron in the crystalline phases, such as diopside, which reduce leakage conductance in ceramics and alleviate the influence of relaxation and space charge polarization on the electrical properties of ceramics. This study provides a new strategy for preparing high-value insulating ceramics from solid waste.