In this study, we report a solid-state synthesis of a novel Ce/Mn co-doped LaAlO3 ceramic with high far infrared emissivity. After detailed analysis of the infrared absorption and emission of the Ce/Mn co-doped LaAlO3 ceramics, we find that the synergistic effect of Ce/Mn co-doping is the key factor to promoting the infrared emission properties of the co-doped perovskite-type ceramic in 8–14 μm range. Compared with the pristine LaAlO3, La0.7Ce0.3Mn0.4Al0.6O3 sample displays the highest emissivity as high as 0.915. From the structural analysis, it is found that the occupation of irregular polyhedrons (A-site) by Ce4+ ion induces the generation of Mn2+ in the octahedral center (B-site), leading to the unit cell volume expansion and obvious lattice deformation. These structural alterations consequently improve the vibration of AlOMn and MnOMn for enhancement of infrared radiation performance. The perovskite-type ceramic, which exhibits a high far infrared emissivity, displays a promising future in energy-saving applications.