In this study, multilayer sandwich heterostructural Ti3C2Tx MXenes decorated with polypyrrole chains have been synthesized successfully via HF etching treatment and in-situ chemical oxidative polymerization approach. The hybrids were investigated as EM wave absorbers for the first time. It is found that the composites consisting of 25 wt% Ti3C2Tx/PPy hybrids in a paraffin matrix exhibit a minimum reflection loss of 49.2 dB (similar to 99.99% absorption) at the thickness of 3.2 mm and a maximum effective absorption bandwidth of 4.9 GHz (12.4-17.3 GHz) corresponding to an absorber thickness of 2.0 mm. Additionally, a broad effective absorption bandwidth of 13.7 GHz (4.3-18.0 GHz) can be reached up by adjusting the thickness from 1.5 to 5.0 mm. Furthermore, the highest effective absorption bandwidth of 5.7 GHz can be reached when the mass fraction is 15 wt%. The enhanced comprehensive electromagnetic wave absorption has close correlation with the well-designed heterogeneous multilayered microstructure, generated heterogeneous interfaces, conductive paths, surface functional groups, localized defects and synergistic effect between laminated Ti3C2Tx and conductive polypyrrole network, which significantly improve impedance matching and attenuation abilities. The superior absorbing performance together with strong absorption and broad bandwidth endows the Ti3C2Tx/PPy hybrids with the potential prospect to be advanced EM wave absorbers. (C) 2017 Elsevier B.V. All rights reserved.