We demonstrated a novel and convenient synthesis of amino-Ti3C2/polyaniline (N-Ti3C2/PANI) composites as high-performance supercapacitors electrode by chemical bonding between organ-like N-Ti3C2 and PANI chains, which were successfully deposited on FTO-glass substrates by a facile two-steps electrochemical reactions. Owing to effective chemical bonds between PANI chains and N-Ti3C2 layers, and well-defined Ti3C2 layers profiting from organ-like structures, it could afford the rapid pathways for charge/ion transfer and prevent the restacking of Ti3C2 layers. Herein, the effects of the electrochemical time of aniline, morphology, structure and electrochemical properties of organ-like N-Ti3C2/PANI composites were explored. Experimental results show that N-Ti3C2 can act as active sites to combine with the amine nitrogens of PANI chains and promote the growth of aniline monomers on the interlamination and surface of Ti3C2 layers. PANI possesses the good pseudocapacitance behavior which can enhance surface area and interlaminar spacing of the Ti3C2 Mxenes. The N-Ti3C2/PANI composites achieve the maximum area capacitance as high as 228 mF cm−2 at a scan rate of 5mVs−1, and almost 85% capacitance retention is obtained after 1000 charging/discharging cycles. Moreover, the facile synthesis of organ-like N-Ti3C2/PANI composite can provide a convenient and green strategy to prepare promising electrode materials for supercapacitors.