The use of semiconductors with a ‘built in’ bias has now become of interest for a growing number of photoactive applications. Using a combination of spectroscopic techniques, gas chromatography in association with mass spectroscopy and NMR, we show that a sample of ferroelectric BaTiO₃ decorated with nanostructured Ag denatures a standard dye molecule (Rhodamine B) via a photocatalytic oxidation mechanism. The photosensitized oxidation was inhibited due to band bending induced by ferroelectric polarisation. In the Ag–BaTiO₃ system we find a slight hypsochromic wavelength shift during the initial stages of degradation (only 3 nm before 80% degradation percentage) and associate this shift with the cleavage of the chromophore structure which pre-empted deethylation. This shift in maximum absorption of the dye molecule did not occur until the later stages of molecule fragmentation. Our major identifiable breakdown intermediate was benzoic acid. A lack of other identifiable fragments during the breakdown of the dye is associated with retention of these fragments on the catalyst as full mineralisation of the dye liberates CO₂.