An unusual approach is reported herein to fabricate magnetic hematite (α-Fe₂O₃) decorated electrochemically reduced graphene oxide (α-Fe₂O₃@erGO) nanocomposite. The method utilizes direct electrochemical reduction of self-assembled, ex-situ synthesized α-Fe₂O₃ anchored GO to erGO (α-Fe₂O₃@erGO) on glassy carbon electrode (GCE) for selective detection of dopamine (DA), an important biomarker of Parkinson's disease. The formation of α-Fe₂O₃@erGO/GCE has been confirmed by XPS and Raman spectroscopy. α-Fe₂O₃@erGO modified GCE exhibits synergistic catalytic activity nearly 2.2 and 5 fold higher than α-Fe₂O₃@GO and other modified electrodes, respectively towards oxidation of DA. The fabricated sensor exhibited linear dynamic ranges over 0.25 − 100 µM in response to DA with a LOD of 0.024 µM (S/N = 3), LOQ of 0.08 µM (S/N = 10), and a sensitivity of 12.56 µA µM^–1 cm^–2. Finally, the practical analytical application of the proposed α-Fe₂O₃@erGO/GCE was investigated for the determination of DA in commercially available pharmaceutical formulation and human serum samples, and showed satisfactory recovery results towards DA.