Abstract We describe here an immobilization method of four Keggin‐type polyoxometalates (POMs) ([H 2 W 12 O 40 ] 6− , [BW 12 O 40 ] 5− [SiW 12 O 40 ] 4− , [PW 12 O 40 ] 3− ) by using the reaction with an ionic liquid, 1‐butyl‐3‐vinylimidazolium (BVIM) bromide. The reaction yields a hybrid material (BVIM‐POM) as a water‐insoluble salt. The chemical structure of both compounds is preserved, as indicated by infrared spectroscopy (FT‐IR), although with a reduced crystallinity (shown by X‐ray diffraction analysis) due to a decrease of water content (shown by thermogravimetric analysis). Cross polarization 1 H‐ 31 P NMR evidenced the presence of BVIM in the structure of (BVIM) 3 [PW 12 O 40 ]. The salt is mixed with carbon powder and Nafion to prepare an ink and casted on glassy carbon electrodes. The electrochemical behavior of immobilized POMs material is preserved. The electrochemical activity for nitrite reduction is measured by cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). It was observed that the reduction current of 10 mM HNO 2 at pH 1 in 0.5 M Na 2 SO 4 is enhanced in the presence of these hybrid materials. DEMS has evidenced the formation of nitrous oxide (N 2 O) at potentials more positive compared to the use of parent POMs in solution.