The management of thermal conductivity is of significant scientific interest, particularly for thermal barrier coatings (TBCs). Multifarious strategies have been used to regulate heat transportation, but it is hard to achieve limit thermal conductivity at elevated temperatures. A systematical investigation of weberite (La1-xGdx)3NbO7 was thus performed, and multiphonon scattering mechanisms were introduced to achieve limit thermal conductivity (0.92 W m−1 K−1). Phonon point defect scattering process accounted for thermal conductivity reduction at low temperatures. Additionally, lattice softening strongly contributed to the reduction of high-temperature thermal conductivity, and solid and stiff chemical bonds were beneficial for inhibiting thermal radiative conductivity. A novel strategy was presented to modify thermal transportation property of weberite RE3NbO7 ceramics. Also, the hardness, toughness, and modulus were improved to promote engineering applications of weberite RE3NbO7. This study also illuminates novel paths for thermal management and mechanical properties manipulation of TBCs, thermoelectric materials, and microelectronics.