In this paper, cordierite ceramics with high far-infrared emission properties are synthesized by a high-temperature solid-phase method using molybdenum tailings and vanadium-titanium magnetite tailings. The microstructure, physical properties and far-infrared emission mechanism of ceramics are investigated. The results show that the ceramics synthesized with 10 wt% molybdenum tailings and 30 wt% vanadium-titanium magnetite tailings have a flexural strength of 67 MPa, a bulk density of 2.531 g/cm3 and a maximum far-infrared emissivity of 0.958 when the sintering temperature is 1200 °C. The crystal phase of the ceramic are 21.4 % cordierite and 58.7 % magnesia-alumina spinel. In the sintering process, the Fe3+ in vanadium-titanium magnetite tailings doped into the cordierite to substitute the Mg2+, which has the similar ionic radius with Fe3+, to form a substitutional solute. Ionic substitution causes the lattice parameters of cordierite larger, reducing the symmetry of the lattice vibrations and leading to lattice distortion. In addition, the composition of a large amount of magnesia-aluminum spinel is attributed to the far-infrared emission properties of ceramics.