Electrochemical behaviors of selected Dawson-type polytungstates including alpha(2)-K-10[P2W15Mo2O6 square] where the symbol 0 designates a vacant site, alpha(2)-K-7[Fe(OH2)P2W15Mo2O61], alpha(2)-K-8[Cu(OH2)P2W15Mo2O61], alpha(1)- and alpha K-2-(8)[ Cu(OH2)P2W17O61], alpha(2)-K-8[Cu(OH2)P2W13Mo4O61], and alpha(2)-K-8[Cu(OH2)P2W12Mo5O61] were investigated by cyclic voltammetry ( CV) coupled with the electrochemical quartz microbalance (EQCM), and the results were completed by atomic force microscopy (AFM) observations of the electrodeposited films. The electrocatalytic abilities of these polyoxometalates (POMs) in the reduction of dioxygen, hydrogen peroxide, and NOx were also assessed by CV and EQCM. It turns out that the remarkable electrocatalysis obtained at the reduction potential of Mo centers within alpha(2)-K-8[Cu(OH2)P2W15Mo2O61], but in a domain where Cu2+ is not deposited, benefits from the assistance of the copper center because such catalysis could not be observed in the absence of Cu2+. EQCM confirms that no copper deposition occurs under the experimental conditions used. Analogous behaviors are encountered in the electrocatalytic reduction of nitrite where assistance by the presence of the Cu2+ center induced the observation of catalysis at the potential location of Mo centers. Finally, the reduction of nitrate is triggered by electrodeposited copper but was remarkably favored by the presence of molybdenum atoms within these polyoxometalates ( POMs). All of the results converge to indicate a cooperative effect between the Mo and Cu centers within these POMs. The various results suggest that copper deposition from these POMs should give morphologically different surfaces. AFMstudies confirm this expectation, and the observed morphologies and sizes of particles were rationalized by taking into account the role of the POM skeleton and its atomic composition in the electrodeposition process.