In this study, large amplitude Fourier transformed alternating current (FTAC) voltammetry has been used to determine the heterogeneous electron-transfer kinetics (k degrees and alpha values) associated with the vanadium [SVW11O40](3-/4-) (V-V/IV, E degrees = 0.050 V vs. Fc/Fc(+), where Fc = ferrocene) and tungsten [SVW11O40](4-/5-) (W-VI/V, E degrees = -1.530 V vs. Fc/Fc(+)) processes in dimethylformamide containing tetrabutylammonium hexafluorophosphate as the supporting electrolyte. At glassy carbon (GC), platinum (Pt), gold (Au) and boron-doped diamond (BDD), the V-V/IV process is kinetically more facile than the W-VI/V one. Excellent simulation-experiment fits were achieved for the V-V/IV process at all electrode materials, and at a supporting electrolyte concentration of 0.1 M, the k degrees value associated with this process increases in the order BDD < Pt approximate to Au < GC. By contrast, at all electrode materials except GC, generally poor simulation-experiment fits were achieved for the W-VI/V process, preventing the data from being analysed quantitatively by FTAC voltammetry. Changing the concentration of supporting electrolyte from 0.1 to 0.5 M has a significant influence on the kinetics, with the k degrees value increasing at GC and decreasing at Pt, Au and BDD. Overall, the findings indicate that differences in density of states do not fully explain the electrode material dependence of the k degrees values and that other factors such as surface functional groups (on GC) and the double layer effect need to be taken into consideration. (C) 2016 Elsevier Ltd. All rights reserved.