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The new 2D Ti3C2T x MXene material is widely studied in the field of supercapacitors. However, the electrochemical performance is discounted due to Ti3C2T x film's compact self‐stacking phenomenon. Therefore, the synthesized flexible self‐supporting Ti3C2T x /graphene composite membrane effectively alleviates this inherent disadvantage. Unlike using the traditional reduction graphene oxide, the structural integrity and large‐sized flakes of graphene are synthesized through anhydrous ferric chloride (FeCl3)‐intercalated natural graphite flakes; the obtained composite membrane with high electron transfer capability due to graphene and Ti3C2T x nanosheets shows fewer defects and faster electrolyte ion transport kinetics due to high porosity and specific surface area. The assembled self‐supporting binder‐free symmetric supercapacitor shows an ultrahigh gravimetric energy density of 13.1 Wh kg−1 at a power density of 75 W kg−1. Herein, a new perspective for the mechanism analysis of inhibiting self‐stacking of MXene is provided.