A Reduced Graphene oxide, Polyaniline protected Reduced Graphene Oxide and Reduced Graphene oxide- Polyaniline / Nafion modified glassy carbon (RGO-PANI / Nf / GCE) electrode was prepared and characterized by UV-Vis, FT-IR, XRD and FESEM with EDX Spectrum. The Reduced Graphene oxide-Polyaniline / Nafion (RGOPANI/ Nf) composite for chromium (VI) electrochemical sensing is described. The electrochemical behaviour of Cr (VI) at the Reduced Graphene oxide-Polyaniline / Nafion composite modified glassy carbon electrode (GCE) was investigated by differential pulse voltammetric method. The results showed that the incorporation of polyaniline with graphene significantly enhanced the electrochemical reactivity and voltammetric response of Cr (VI). In addition, Nafion acts as an effective solubilizing agent and antifouling coating in the fabrication of the modified electrode. This electrochemical sensor exhibits excellent analytical performance for Cr (VI) detection at physiological pH with detection limit of 2.1×10−7 M, linear range of 1–100_M and reproducibility of 3.6% relative standard deviation.