In this study, a new inorganic-organic hybrid compound consisting of a Keggin type polyoxometalate, H4SiW12O40 (SiW12), and Nile blue (NB) was synthesized and characterized. The (NB)(2)H2SiW12O40 (NB2SiW12) hybrid compound was characterized by Fourier transform infrared (FT-IR), elemental (CHNS) analysis, UV-Vis and thermogravimetry techniques, and used as a bulk modifier to fabricate a chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the newly NB2SiW12 composite CPE was analyzed by cyclic voltammetry, and the electrode was applied for nitrite reduction, exhibiting high electrocatalytic activity. Determination of nitrite by fixed potential amperometry was done under various experimental conditions and, at the optimum conditions, the linear response ranged from 5 to 1200 mu M with a high sensitivity of and a low detection limit. The electrode has the remarkable advantage of surface renewal owing to bulk modification, as well as simple preparation, good mechanical and chemical stability and reproducibility. No noticeable interferences from other ionic species usually found in natural water were observed. The new developed electrode has been successfully applied for detection of nitrite in real water samples. (C) 2013 Published by Elsevier B.V.