One, two, three and four electron reduced forms of alpha-[P(2)W(18)O(62)](6) in aqueous acidic electrolyte media have been selectively generated by bulk electrolysis from a solution that has an initial pH of 3.6. The reactivities of the reduced polyoxometalate anions and identities of products formed in the presence and absence of dioxygen have been assessed via oxygen and hydrogen Clark-type electrodes, a pH electrode and rotating disk electrode voltammetry. [P(2)W(18)O(62)](7) is stable to protons but is slowly oxidized by dioxygen (timescale: hours to days) back to [P(2)W(18)O(62)](6). In contrast, [P(2)W(18)O(62)](8) reacts more rapidly with O(2) and slowly with H(+), whereas generation of the [P(2)W(18)O(62)](9) and [P(2)W(18)O(62)] (10) anion is accompanied by a large increase in pH and rapid reaction with O(2) or, in its absence, with H(+). Consequently, it is concluded that photocatalytic reactions based upon [P(2)W(18)O(62)](6) chemistry are only likely to be of significance if [P(2)W(18)O(62)](9) or more highly reduced species are generated and form part of the catalytic cycle. (C) 2011 Elsevier B.V. All rights reserved.