Titanium dioxide (TiO2) nanoparticles of both anatase and rutile phases were synthesized by hydrothermal treatment of microemulsions, and their photocatalytic activity for wet oxidation of phenol was studied. The only difference between the two syntheses used was that different acids were added to the microemulsions, making direct comparison of the catalytic activity of the two polymorphs possible. If hydrochloric acid was used, the rutile structure formed, and if nitric acid was used, anatase formed. The phase stability of the microemulsion was studied and according to conductivity and turbidity measurements the idea of a direct template effect could be discarded during the hydrothermal treatment. However, an initial size-templating phenomenon is possible during the mixing step. The particles, which were in the size range of a few nanometers were characterized with N-2-adsorption; XRD, SEM, and XPS. The activity of the two polymorphs for the photocatalytic oxidation of phenol in water was examined. It was shown that the rutile phase initially decomposed phenol much faster and follows a first-order process reasonably well (k = 4 x 10(-5) s(-1)). The photodecomposition process using the anatase phase led, however, to a much more rapid overall degradation following an initial slower rate of phenol oxidation. The results indicate that the observed difference of the photodecomposition process for the two TiO2 phases is due to the formation of different intermediates.