In this study, a 0.25LiFe5O8–0.75Li2ZnTi3O8 solid solution ceramic was developed via the solid-state reaction method. Its phase evolution, microstructure, and sintering behavior were investigated and it was found that the 25 mol.% LiFe5O8 phase is almost fully soluble in Li2ZnTi3O8, and only the Li2ZnTi3O8 type spinel phase was formed in the 0.25LiFe5O8–0.75Li2ZnTi3O8 ceramic. The ceramic sample sintered at 1050°C for 2 h was found to possess both good magnetic properties and dielectric properties in the frequency range from 1 to 10 MHz, with permeability between 38.2 and 15 and magnetic loss tangent between 0.25 and 0.75, permittivity between 19.6 and 19.3 and dielectric loss tangent between 8 × 10−3 and 2 × 10−3. The sample also possesses good microwave dielectric properties with a relative permittivity of 19.1, a high quality factor (Qf) ~11,770 GHz (at 6.84 GHz). The ceramic is a novel magneto-dielectric ceramic with both high permeability and good dielectric properties, which might be a good candidate for the applications in novel electronic devices.