A kind of graphene/polyaniline hybrid hollow capsule was fabricated via Pickering emulsion using ionic liquid-modified reduced graphene oxide (rGO-IL) Pickering emulsifier. In our strategy, rGO-IL was first prepared and employed to stabilize the oil phase containing aniline to prepare the stable and uniform Pickering emulsion. Upon the polymerization of aniline at the oil/water interface, ionic liquid functionalized graphene/polyaniline hollow spheres (rGO-IL/PANI HS) were obtained. The functionalization of rGO by ionic liquid can not only adjust the wettability of rGO, but also avoid reducing its conductivity. The wettability of rGO-IL is adjusted by adjusting the modification degree of graphene by IL-NH2. The influence of wettability and concentration of rGO-IL as well as oil-water ratio on the properties of Pickering emulsion was explored. At the same time, the effect of aniline addition on the electrochemical performance of rGO-IL/PANI HS was also studied. The Pickering emulsions stabilized by rGO-IL were observed by super deep scene 3D microscope. According to the emulsion droplet morphology and particle size distribution, the optimal preparation conditions were obtained. The chemical structure and morphology of rGO-IL/PANI HS were analyzed by FT-IR, Raman spectrum and scanning electron microscope. The results show that the final product prepared from the rGO-IL-stabilized Pickering emulsion has spherical shape, and an obvious hollow structure could be observed from the breakage. The capacitance performance of rGO-IL/PANI HS was explored by cyclic voltammetry and galvanostatic charge-discharge. The specific capacitance of rGO-IL/PANI HS is able to reach a maximum of 451.8 F/g, which is nearly double that of two-dimensional rGO-IL/PANI materials (227 F/g). In addition, the prepared rGO-IL/PANI HS also shows excellent rate performance. When the current density is increased from 0.5 A/g to 10 A/g, the capacitance retention rate of rGO-IL/PANI HS is as high as 92.4%, much higher than 46.5% of two-dimensional materials.