In this work, multi-walled carbon nanotube (MWNT) bonded graphene (M-GR) composites were prepared using the chemical reduction of graphite oxide (GO) and acid treated MWNTs with different ratios. The M-GR/polyaniline (PANI) nanocomposites (M-GR/PANI) were prepared using oxidation polymerization. The effect of the M-GR ratio on the electrochemical performances of the M-GR/PANI was investigated. It was found that the substrate 2D graphene was coated with 1D MWNTs by chemical reduction and the M-GR was further coated with PANI, leading to increased electrical properties by the π–π interaction between the M-GR and PANI. In addition, the electrochemical performances, such as the current density, charge–discharge, and specific capacitance of the M-GR/PANI were higher than those of graphene/PANI and the highest specific capacitance (1118F/g) of the composites was obtained at a scan rate of 0.1A/g for the PANI containing a 0.5 M-GR ratio compared to 191F/g for the graphene/PANI. The dispersion of the MWNTs onto the graphene surface and the ratio of M-GR had a pronounced effect on the electrochemical performance of the PANI-based composites, which was attributed to the highly conductive pathway created by the M-GR incorporated in the PANI-based composites and the synergistic effect between M-GR and PANI.