Anodes play an important role in the extracellular electron transfer (EET) process in microbial fuel cells (MFCs). Herein, polyaniline modified multilayer MXene (PANI-MXene) on carbon cloth was used as an anode to improve the EET efficiency. The PANI-MXene was formed by the electrostatic interaction between the negatively charged groups of MXene and the positively charged protonated amino groups of PANI to enhance the bacterial adhesion and biofilm formation. The MFCs obtained a high maximum power density (737.3 mW·m-2) with the efficient EET process. This work provides a meaningful way to decorate anodes using binder-free modifiers for MFCs.