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We have used photodissociation spectroscopy to probe the electronic structure and photoreduction of Au(III) in gas-phase complexes containing Cl$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ and OH$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$. The gas-phase electronic spectrum of [AuCl$4$]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ closely resembles the aqueous solution spectrum, showing a lack of strong solvatochromic shifts. Substitution of Cl$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ ligands with OH$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ results in a strong blue shift, in agreement with ligand-field theory. Upon excitation, [AuCl$4$]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ can dissociate by loss of either one or two neutral Cl atoms, resulting in the reduction of gold from Au(III) to Au(II) and Au(I) respectively. The hydroxide substituted complex, [AuCl$2$(OH)$2$]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$, demonstrates similar behavior but the only observable fragment channel is the loss of two neutral OH ligands, leading only to Au(I).