A novel modified glassy carbon electrode (GCE) was successfully fabricated with a tetra-component nanocomposite consisting of (1,1′-(1,4-butanediyl)dipyridinium) ionic liquid (bdpy), SiW₁₁O₃₉Ni(H₂O) (SiW₁₁Ni) Keggin-type polyoxometalate (POM), and phosphorus-doped electrochemically reduced graphene oxide (P-ERGO) by electrodeposition technique. The (bdpy)SiW₁₁Ni/GO hybrid nanocomposite was synthesized by a one-pot hydrothermal method and characterized by UV-vis absorption, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) analysis, thermogravimetric-differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM). The morphology, electrochemical performance, and electrocatalysis activity of the nanocomposite modified glassy carbon electrode ((bdpy)SiW₁₁Ni/P-ERGO/GCE) were analyzed by field emission scanning electron microscopy (FE-SEM) coupled with energy-dispersive X-ray spectroscopy (EDS), cyclic voltammetry (CV), square wave voltammetry (SWV), and amperometry, respectively. Under the optimum experimental conditions, the as-prepared sensor showed high sensitivity of 28.1 μA mM⁻¹ and good selectivity for iodate (IO₃⁻) reduction, enabling the detection of IO₃⁻ within a linear range of 10–1600 μmol L⁻¹ (R² = 0.9999) with a limit of detection (LOD) of 0.47 nmol L⁻¹ (S/N = 3). The proposed electrochemical sensor exhibited good reproducibility, and repeatability, high stability, and excellent anti-interference ability, as well as analytical performance in mineral water, tap water, and commercial edible iodized salt which might provide a capable platform for the determination of IO₃⁻.