Polymers and transition-metal oxides have gained great interest as a photocatalyst in environmental remediation. They could be modified with each other in order to improve their activity. Here, a sunlight-responsive hierarchically structured ternary composite of nickel oxide, polyaniline, and reduced graphene oxide (NiO@PANI/RGO) has been synthesized and employed as a catalyst for dye [methylene blue (MB)] degradation. PANI/GO synthesized by interfacial polymerization acts as a matrix for the growth of NiO using a microemulsion solvothermal method, ensuing an in situ reduction of graphene oxide during the formation of a hierarchical NiO@PANI/RGO composite. Morphological studies of the as-synthesized NiO@PANI/RGO composite reveal fine NiO (10 nm) nanoparticles intercalated between the uniformly grown PANI spines (50-60 nm) over the RGO surface. The optical band gap of ∼1.9 eV calculated from the UV-vis spectrum illustrates the extended light absorption range for the NiO@PANI/RGO photocatalyst. The efficiency of 98% MB degradation within 11 min with the degradation rate constant 0.086 min for NiO@PANI/RGO has surpassed any other report on metal oxide/graphene-based ternary composites. Overall, this work could pave the way for the fabrication of futuristic hierarchical structured ternary nanocomposites as an efficient photocatalyst and facilitate their application in the environmental protection issues.