A robust and stable film comprising n-octylpyridinum hexafluorophosphate ([C8Py][PF6]) and 1:12 phosphomolybdic acid (PMo12) was prepared on glassy carbon electrodes modified with multiwall carbon nanotubes (GCE/MWCNTs) by dip-coating. The cyclic voltammograms of the GCE/MWCNTs/[C8Py][PF6]-PMo12 showed three well-defined pairs of redox peaks due to the PMo12 system. The surface coverage for the immobilized PMo12 and the average values of the electron transfer rate constant for three pairs of redox peaks were evaluated. The GCE/MWCNTs/[C8Py][PF6]-PMo12 showed great electrocatalytic activity towards the reduction of H2O2 and iodate. The kinetic parameters of the catalytic reduction of hydrogen peroxide and iodate at the electrode surface and analytical features of the sensor for amperometric determination of hydrogen peroxide and iodate were evaluated. (C) 2010 Elsevier Ltd. All rights reserved.