Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic pollutants and their low water solubility limits their degradation in aqueous solution. The presence of water-miscible solvent such as acetone can increase the water solubility of PAHs, however acetone will also affect the degradation of PAH. In this study the effects of acetone on the photocatalytic degradation efficiency and pathways of 5 selected PAHs, namely naphthalene (2 rings), acenaphthylene (3 rings), phenanthrene (3 rings), anthracene (3 rings) and benzoaanthracene (4 rings) were investigated. The Microtox ® toxicity test was used to determine whether the PCO system can completely detoxify the parental PAHs and its intermediates. The addition of 16% acetone can greatly alter the degradation pathway of naphthalene and anthracene. Based on intermediates identified from degradation of the 5 PAHs, the location of parental PAHs attacked by reactive free radicals can be correlated with the localization energies of different positions of the compound. For toxicity analysis, irradiation by UV light was found to induce acute toxicity by generating intermediates/degradation products from PAHs and possibly acetone. Lastly, all PAHs (10 mg l −1) can be completely detoxified by titanium dioxide (100 mg l −1) within 24 h under UVA irradiation (3.9 mW cm −2).