In this work, NiCoAl-layered double hydroxide (LDH)/MXene was successfully prepared through straightforward hydrothermal method. NiCoAl-LDH was tightly and uniformly coated on MXene, forming a kind of porous structure. NiCoAl-LDH/MXene exhibited the (002) (012) (105) (100) crystal planes of hydrotalcite reflection. NiCoAl-LDH/MXene also showed superior catalytic oxygen reduction reaction (ORR) in response current according to electrochemical test (cyclic voltammetry (CV) etc.). The maximum power density and output voltage of NiCoAl-LDH/MXene as cathode in microbial fuel cell (MFC) was 362.404 mW/m2 and 450 mV, respectively, which was 1.54 times of MXene-MFC (234.256 mW/m2) and 1.71 times of NiCoAl-LDH-MFC (211.56 mW/m2). The results indicated that NiCoAl-LDH/MXene was a kind of potential cathode catalyst for MFC and was full of future application.