Abstract The microstructure dependent electromagnetic interference (EMI) shielding properties of nano-layered Ti 3 AlC 2 ceramics were presented in this study by comparing the shielding properties of various Ti 3 AlC 2 ceramics with distinct microstructures. Results indicate that Ti 3 AlC 2 ceramics with dense microstructure and coarse grains are more favourable for superior EMI shielding efficiency. High EMI shielding effectiveness over 40 dB at the whole Ku-band frequency range was achieved in Ti 3 AlC 2 ceramics by microstructure optimization, and the high shielding effectiveness were well maintained up to 600 °C. A further investigation reveals that only the absorption loss displays variations upon modifying microstructure by allowing more extensive multiple reflections in coarse layered grains. Moreover, the absorption loss of Ti 3 AlC 2 was found to be much higher than those of highly conductive TiC ceramics without layered structure. These results demonstrate that nano-layered MAX phase ceramics are promising candidates of high-temperature structural EMI shielding materials and provide insightful suggestions for achieving high EMI shielding efficiency in other ceramic-based shielding materials.