Electrocatalysts play an important role in the cathodic Oxygen Reduction Reaction (ORR) of fuel cells. Because of the high cost, poor cycle stability and methanol tolerance, the commercial Pt/C catalysts have been seriously restricted during large-scale application and development in electrochemical devices. The development of non-noble metal ORR catalysts is one of the effective ways to achieve fuel cell cost reduction and performance improvement at the same time. In this work, Ti4O7/MXene nanocomposites were synthesized through hydrothermal followed by carbothermal reduction reactions. Such catalysts exhibit large electrochemical active surface area (ECSA = 215.74 cm2) and excellent ORR catalytic activity in alkaline media. The initial potential and half-wave potential were confirmed to be 0.91 V and 0.72 V with the electron transfer number of 3.3. In addition, the Ti4O7/MXene catalysts have better cyclic stability and methanol tolerance than commercial Pt/C catalyst. This study provides a new idea and method for the innovative preparation of MXene-based composite electrocatalysts.