Photochromism of [SiW11O39Ni( X)](6-) as a tetraheptylammonium salt in various solvents under broadband UV light is observed in the presence of alcohols. The reaction proceeds faster with benzyl alcohol than with ethanol. Benzaldehyde is identified as the oxidized product of benzyl alcohol. Photochemistry is a reliable means to produce stable reduced transition metal substituted heteropoly tungstates in nonpolar media, where they hold promise as multielectron reduction catalysts. Preliminary reactivity toward CO2 reduction is demonstrated.