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 pm 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 Al-O-Mn and Mn-O-Mn 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.