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The rate of photocatalytic oxidation of polystyrene over 0.1 wt% copper-doped TiO2 catalyst spin coated onto a flat substrate is investigated as a function of the catalyst deposition spin speed and, hence, film thickness. Photoinduced force microscopy and photoelectron spectroscopy show no evidence of any products of the photocatalytic oxidation remaining on the surface after reaction. The oxidation reaction shows no discernible dependence on spin speed; it is close to zero order in polystyrene concentration and exhibits a ½ life almost 50 times greater than the equivalent photocatalytic oxidation of stearic acid on the same catalysts. No difference between the rate of decay of the aliphatic and aromatic hydrogens of the polymer was observed, suggesting that once a polymer chain begins oxidising, subsequent steps are relatively rapid. This is consistent with the rate-determining step being dependent on the extent of coordination to the surface, which is much more favourable with stearic acid because of its carboxylic group.