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[Display omitted] • Controllable preparation of CeO 2 @C core–shell nanorods/nanofibers. • Optimizing the composition, structure, and properties of the composites. • A synchronous enhancement of heat conductance and EMW absorption. • Revealing the interfaces and oxygen vacancy dependent of performance. High-performance thermally conductive-microwave absorbing integrated materials are highly required to mitigate the severe electromagnetic pollution and overheating generated in electronic devices. However, the incompatibility between thermal conduction and microwave absorption impedes their collaborative development. Herein, an adjustment strategy for interface- and oxygen-vacancy-linkage was adopted to rationally construct CeO 2 @C core–shell nanorods/nanofibers (CSNRs/NFs) and cooperatively boost their electrical, thermal, and microwave absorption properties. A hydrothermal-annealing technique was employed to synthesize CeO 2 @C CSNRs/NFs. Their core–shell structure, oxygen vacancies/lattice defects, and length-to-diameter ratio were accurately adjusted by changing the annealed temperature (T a) and toluene volume (V). The CeO 2 @C CSNRs/NFs produced under T a = 600 °C and V = 1.5 mL exhibit high thermal conductivity (TC = 2.94 W/(m·K)) at a small load of 40 wt%. The large TC is mainly due to the weak phonon defect/interface scattering and electron/phonon co-transfer in a 3D continuous path consisting of a 1D structure. Furthermore, the CeO 2 @C CSNRs/NFs display strong microwave absorption (EAB max /d = 3.27 GHz/mm; RL min =− 50.98 dB) due to their various polarizations, tunable conduction loss, and multiple internal reflections. These results demonstrate that the CeO 2 @C CSNR/NFs are an ideal multifunctional material that protects against concurrent EM interference and excess heat in electronic packaging materials. [ABSTRACT FROM AUTHOR]