A family of four polyoxovanadate-alkoxide (POV-alkoxide) clusters was prepared and electrochemical techniques were used to evaluate diffusion coefficients and electron transport across a range of oxidation states. Synthetic routes were developed to increase the alkyl chain length of the [V6O7(OR)(12)] cores, increasing R from the previously reported R = CH3, C2H5 to R = C3H7, C4H9. Whereas increasing chain length may enhance solubility, such modifications may also hinder diffusion and electron transfer by shielding the core, thus we experimentally determined these parameters using both cyclic voltammetry and rotating disk voltammetry. Increasing the alkyl chain length of the POV-alkoxide nanostructures from methoxide to butoxide changes the solubility from 0.205 to 0.297 M in acetonitrile. Although some variations in diffusion coefficients and heterogeneous electron transfer rate constants were observed across the suite of oxidation states from species to species, they range from 0.14 x 10(-5) cm(2)/s to 2.24 x 10-5 cm2/s for D-0 and 0.56 x 10(-3) cm/s to 209.00 x 10(-3) cm/s for k(het). An increased chain length did not result in lower diffusion coefficients. Thus, we conclude that between C1 and C4 chains, no shielding of the redox core occurs, nor is transport through solution systematically hindered. (c) 2019 The Electrochemical Society.