The catalytic photodegradation of phenol and 4-chlorophenol with white and W Light over TiO2, BaTi4O9 and Hollandite catalysts has been studied in our laboratories. BaTi4O9 and Hollandite catalysts were prepared by solid state reaction at 900 degrees C and 1200 degrees C, respectively. All the catalysts were characterized by different techniques such as surface area measurements by the BET method, atomic absorption spectroscopy and XRD. Photodegradation reaction experiments were monitored by HPLC analysis. The reaction intermediates : hydroquinone and 1,4-benzoquinone were identified by GC-MS analysis. The photocatalytic activities of these catalysts in the degradation of phenol and 4-chlorophenol were evaluated in comparison with titanium oxide. Experimental results showed that BaTi4O9 and Hollandite catalysts exhibit small photocatalytic activity as compared with TiO2.