Three new inorganic-organic hybrid compounds based on the Keggin/Dawson POMs, [Cu-2(Htib)(2) (alpha-SiW12O40)] (1), [Cu(Htib)(2)(H(2)tib)(2) (H2O)(4)(alpha-HBW12O40)(2)]center dot 8H(2)O (2), and [Cu-2(H(2)tib)(4)(H2O)(2)(alpha-HP2W18O62)(2)]center dot 14H(2)O (3) (tib =1,3,5-tris(i-imidazoly) benzene), have been obtained through hydrothermal methods. X-ray structural analyses show that compounds 1-3 are constructed from Cu-tib modified Keggin/Dawson POMs. Compounds 1-3 have been employed to fabricate bulk-modified carbon paste electrode (CPE) (noted as n-CPEs, n = 1-3) to study their electrochemical properties. Cyclic voltammetries of n-CPEs (n = 1-3) display bifunctional electrocatalytic activities toward reduction of nitrite and oxidation of ascorbic acid. (C) 2015 Published by Elsevier Ltd.