Ferrocene was linked to polyvinyl alcohol polymer via ethylene dioxi‐bis‐ethylamine (PV‐Fc) spacer and the synthesized redox polymer was characterised by FT‐IR and H1NMR spectroscopy. Aqueous solution of PVA‐Fc was used to prepare its silica composite with tetraethylorthosilicate (TEOS). The immobilized PVA‐Fc/silica film showed E0 about 0.245 V and apparent diffusion coefficient was measured to be 2.76×10−8 cm2 s−1. The ferrocene with flexible spacer in PVA‐Fc/silica film showed an excellent electrocatalytic activity towards the sulfite oxidation at 0.35 V, that was minimum 0.3 V negative shift of the overpotential than the bare electrode. The effect of the interfearing species like acetate, ammonium, carbonate, phosphate and sulfate has been checked for the sulfite detection. Under the optimized conditions the prepared composite showed sulfite oxidation in the linear range of 5×10−7 M to 1×10−4 M and lower detection limits of 1.5×10−7 M.